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OLEFIN METATHESIS CATALYSTS

20210053043 ยท 2021-02-25

    Inventors

    Cpc classification

    International classification

    Abstract

    This invention relates generally to metathesis catalysts and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in Z and E selective olefin metathesis reactions. The invention has utility in the fields of organometallics and organic synthesis.

    Claims

    1.-8. (canceled)

    9. A compound of formula (I) ##STR00083## wherein: X is O or S; Y is O or S; Z is N or CR.sup.32; W is O, NR.sup.33 or S; R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring; R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring; R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.16 may form an optionally substituted polycyclic ring; R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring; R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.18 may form an optionally substituted polycyclic ring; R.sup.18 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.17 may form an optionally substituted polycyclic ring; R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.28 is H, optionally substituted C.sub.1-8 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.33 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    10. The compound of claim 9 wherein X is O or S; Y is O or S; Z is N or CR.sup.32; W is O, NR.sup.33 or S; R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring; R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring; R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.18 may form a polycyclic ring; R.sup.18 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.17 may form a polycyclic ring; R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.28 is H, optionally substituted C.sub.1-8 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.33 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    11. The compound of claim 9 wherein X is S; Y is S; Z is N or CR.sup.32; W is O; R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring; R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring; R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.16 may form an optionally substituted polycyclic ring; R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring; R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.18 may form an optionally substituted polycyclic ring; R.sup.18 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.17 may form an optionally substituted polycyclic ring; R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.28 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    12. The compound of claim 9 wherein X is S; Y is S; Z is N; W is O; R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring; R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring; R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.16 may form an optionally substituted polycyclic ring; R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring; R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.18 may form an optionally substituted polycyclic ring; R.sup.18 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.17 may form an optionally substituted polycyclic ring; R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.28 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    13. The compound of claim 9 wherein X is S; Y is S; Z is CR.sup.32; W is O; R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring; R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring; R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.16 may form an optionally substituted polycyclic ring; R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring; R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring; R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.17 may form an optionally substituted polycyclic ring; R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.28 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    14. The compound of claim 9 wherein X is S; Y is S; ##STR00084## of Formula (I) is ##STR00085## ##STR00086## of Formula (I) is ##STR00087## R.sup.20 is H; and R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.16 may form an optionally substituted polycyclic ring; R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring; R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.18 may form an optionally substituted polycyclic ring; R.sup.18 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle,

    15. The compound of claim 9, wherein ##STR00088## of Formula (I) is ##STR00089## ##STR00090## of Formula (I) ##STR00091## R.sup.20 is H; and ##STR00092## of Formula (I) is ##STR00093## ##STR00094##

    16. The compound of claim 15, wherein ##STR00095## of Formula (I) is ##STR00096##

    17. A method for performing a cross metathesis reaction, comprising: contacting a first olefin reactant with a second olefin reactant in the presence of a compound according to claim 9, under conditions effective to promote the formation of at least one cross metathesis product.

    18. The method according to claim 17, wherein the first olefin reactant and the second olefin reactant are the same.

    19. The method according to claim 17, wherein the first olefin reactant and the second olefin reactant are different.

    20. The method according to claim 17, wherein the first olefin reactant and the second olefin reactant are each in a Z-configuration.

    21. The method according to claim 20, wherein the at least one cross metathesis product is greater than about 80% Z.

    22. The method according to claim 17, wherein the first olefin reactant and the second olefin reactant are each in an E-configuration.

    23. The method according to claim 22, wherein the at least one cross metathesis product is greater than about 80% E.

    Description

    DETAILED DESCRIPTION

    Terminology and Definitions

    [0034] Unless otherwise indicated, the invention is not limited to specific reactants, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments and is not to be interpreted as being limiting.

    [0035] As used in the specification and the appended claims, the singular forms a, an, and the include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an -olefin includes a single -olefin as well as a combination or mixture of two or more -olefins, reference to a substituent encompasses a single substituent as well as two or more substituents, and the like.

    [0036] As used in the specification and the appended claims, the terms for example, for instance, such as, or including are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention, and are not meant to be limiting in any fashion.

    [0037] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings.

    [0038] The term alkyl as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (Pr or n-Pr), isopropyl (i-Pr), n-butyl (Bu or n-Bu), isobutyl (i-Bu), t-butyl (t-Bu), octyl (Oct), decyl, and the like, as well as cycloalkyl groups such as cyclopentyl (Cp), cyclohexyl (Cy) and the like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 8 carbon atoms. The term lower alkyl refers to an alkyl group of 1 to 6 carbon atoms, and the specific term cycloalkyl refers to a cyclic alkyl group, typically having 3 to 8, preferably 5 to 7, carbon atoms. The term substituted alkyl refers to alkyl substituted with one or more substituent groups, and the terms heteroatom-containing alkyl and heteroalkyl refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms alkyl and lower alkyl include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.

    [0039] The term alkylene as used herein refers to a difunctional linear, branched, or cyclic alkyl group, where alkyl is as defined above.

    [0040] The term alkenyl as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Preferred alkenyl groups herein contain 2 to about 12 carbon atoms. The term lower alkenyl refers to an alkenyl group of 2 to 6 carbon atoms, and the specific term cycloalkenyl refers to a cyclic alkenyl group, preferably having 3 to 8 carbon atoms. The term substituted alkenyl refers to alkenyl substituted with one or more substituent groups, and the terms heteroatom-containing alkenyl and heteroalkenyl refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms alkenyl and lower alkenyl include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively.

    [0041] The term alkenylene as used herein refers to a difunctional linear, branched, or cyclic alkenyl group, where alkenyl is as defined above.

    [0042] The term alkynyl as used herein refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term lower alkynyl refers to an alkynyl group of 2 to 6 carbon atoms. The term substituted alkynyl refers to alkynyl substituted with one or more substituent groups, and the terms heteroatom-containing alkynyl and heteroalkynyl refer to alkynyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms alkynyl and lower alkynyl include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively.

    [0043] The term alkynylene as used herein refers to a difunctional alkynyl group, where alkynyl is as defined above.

    [0044] The term alkoxy as used herein refers to an alkyl group bound through a single, terminal ether linkage; that is, an alkoxy group may be represented as O-alkyl where alkyl is as defined above. A lower alkoxy group refers to an alkoxy group containing 1 to 6 carbon atoms. Analogously, alkenyloxy and lower alkenyloxy respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and alkynyloxy and lower alkynyloxy respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.

    [0045] The term aryl as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 6 to 10 carbon atoms. Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl (Ph), naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, phenanthryl and the like. Substituted aryl refers to an aryl moiety substituted with one or more substituent groups, and the terms heteroatom containing aryl and heteroaryl refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail herein.

    [0046] The term aryloxy as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein aryl is as defined above. An aryloxy group may be represented as O-aryl where aryl is as defined above. Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 6 to 10 carbon atoms. Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

    [0047] The term alkaryl refers to an aryl group with an alkyl substituent, and the term aralkyl refers to an alkyl group with an aryl substituent, wherein aryl and alkyl are as defined above. Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms. Alkaryl groups include, without limitation, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms alkaryloxy and aralkyloxy refer to substituents of the formula OR wherein R is alkaryl or aralkyl, respectively, as just defined.

    [0048] The term acyl refers to substituents having the formula (CO)-alkyl, (CO)-aryl, (CO)-aralkyl, (CO)-alkaryl, (CO)-alkenyl, or (CO)-alkynyl, and the term acyloxy refers to substituents having the formula O(CO)-alkyl, O(CO)-aryl, O(CO)-aralkyl, O(CO)-alkaryl, O(CO)-alkenyl, or (CO)-alkynyl wherein alkyl, aryl, aralkyl, alkaryl, alkenyl, and alkynyl are as defined above. The acetoxy group (O(CO)CH.sub.3; often abbreviated as OAc) is a common example of an acyloxy group.

    [0049] The terms cyclic and ring refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic. The term alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic or polycyclic.

    [0050] The terms polycyclic ring refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that have at least two closed rings tethered, fused, linked via a single bond or bridged. Polycyclic rings include without limitation naphthyl, biphenyl, phenanthryl and the like.

    [0051] The terms halo and halogen and halide are used in the conventional sense to refer to a fluoro, chloro, bromo, or iodo substituent.

    [0052] Hydrocarbyl refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like. The term lower hydrocarbyl refers to a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the term hydrocarbylene refers to a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term lower hydrocarbylene refers to a hydrocarbylene group of 1 to 6 carbon atoms. Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups, and the terms heteroatom-containing hydrocarbyl and heterohydrocarbyl refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, substituted hydrocarbylene refers to hydrocarbylene substituted with one or more substituent groups, and the terms heteroatom-containing hydrocarbylene and heterohydrocarbylene refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term hydrocarbyl and hydrocarbylene are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.

    [0053] The term heteroatom-containing as in a heteroatom-containing hydrocarbyl group refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur. Similarly, the term heteroalkyl refers to an alkyl substituent that is heteroatom-containing, the term heterocyclic refers to a cyclic substituent that is heteroatom-containing, the terms heteroaryl and heteroaromatic respectively refer to aryl and aromatic substituents that are heteroatom-containing, and the like. It should be noted that a heterocyclic group or compound may or may not be aromatic, and further that heterocycles may be monocyclic, bicyclic, or polycyclic as described above with respect to the term aryl. Examples of heteroalkyl groups include without limitation alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include without limitation pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples of heteroatom-containing alicyclic groups include without limitation pyrrolidino, morpholino, piperazino, piperidino, etc.

    [0054] By substituted as in substituted hydrocarbyl, substituted alkyl, substituted aryl, and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation: functional groups referred to herein as Fn, such as halo, hydroxyl, sulfhydryl, C.sub.1-C.sub.24 alkoxy, C.sub.2-C.sub.24 alkenyloxy, C.sub.2-C.sub.24 alkynyloxy, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.24 aralkyloxy, C.sub.6-C.sub.24 alkaryloxy, acyl (including C.sub.2-C.sub.24 alkylcarbonyl (CO-alkyl) and C.sub.6-C.sub.24 arylcarbonyl (CO-aryl)), acyloxy (O-acyl, including C.sub.2-C.sub.24 alkylcarbonyloxy (OCO-alkyl) and C.sub.6-C.sub.24 arylcarbonyloxy (OCO-aryl)), C.sub.2-C.sub.24 alkoxycarbonyl ((CO)O-alkyl), C.sub.6-C.sub.24 aryloxycarbonyl ((CO)O-aryl), halocarbonyl (CO)X where X is halo), C.sub.2-C.sub.24 alkylcarbonato (O(CO)O-alkyl), C.sub.6-C.sub.24 arylcarbonato (O(CO)O-aryl), carboxy (COOH), carboxylato (COO.sup.), carbamoyl ((CO)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 haloalkyl)), di-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 haloalkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.5-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), thiocarbamoyl ((CS)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.5-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), carbamido (NH(CO)NH.sub.2), cyano(CN), cyanato (OCN), thiocyanato (SCN), isocyanate (NisCisO), thioisocyanate (NisCisS), formyl ((CO)H), thioformyl ((CS)H), amino (NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted amino (NH(C.sub.1-C.sub.24 alkyl), di-(C.sub.1-C.sub.24 alkyl)-substituted amino ((N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted amino (NH(C.sub.5-C.sub.24 aryl), di-(C.sub.5-C.sub.24 aryl)-substituted amino (N(C.sub.5-C.sub.24 aryl).sub.2), C.sub.2-C.sub.24 alkylamido (NH(CO)-alkyl), C.sub.6-C.sub.24 arylamido (NH(CO)-aryl), imino (CRisNH where, R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), C.sub.2-C.sub.20 alkylimino (CRisN(alkyl), where R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), arylimino (CRisN(aryl), where R includes without limitation hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), nitro (NO.sub.2), nitroso (NO), sulfo (SO.sub.2OH), sulfonato (SO.sub.2O), C.sub.1-C.sub.24 alkylsulfanyl (S-alkyl; also termed alkylthio), C.sub.5-C.sub.24 arylsulfanyl (S-aryl; also termed arylthio), C.sub.1-C.sub.24 alkylsulfinyl ((SO)-alkyl), C.sub.5-C.sub.24 arylsulfinyl ((SO)-aryl), C.sub.1-C.sub.24 alkylsulfonyl (SO.sub.2-alkyl), C.sub.1-C.sub.24 monoalkylaminosulfonyl (SO.sub.2N(H) alkyl), C.sub.1-C.sub.24 dialkylaminosulfonyl (SO.sub.2N(alkyl).sub.2), C.sub.5-C.sub.24 arylsulfonyl (SO.sub.2-aryl), boryl (BH.sub.2), borono (B(OH).sub.2), boronato (B(OR).sub.2 where R includes without limitation alkyl or other hydrocarbyl), phosphono (P(O)(OH).sub.2), phosphonato (P(O)(O.sup.).sub.2), phosphinato (P(O)(O.sup.)), phospho (PO.sub.2), phosphino (PH.sub.2), silyl (SiR.sub.3 wherein R is hydrogen or hydrocarbyl), and silyloxy (O-silyl); and the hydrocarbyl moieties C.sub.1-C.sub.24 alkyl (preferably C.sub.1-C.sub.12 alkyl, more preferably C.sub.1-C.sub.6 alkyl), C.sub.2-C.sub.24 alkenyl (preferably C.sub.2-C.sub.12 alkenyl, more preferably C.sub.2-C.sub.6 alkenyl), C.sub.2-C.sub.24 alkynyl (preferably C.sub.2-C.sub.12 alkynyl, more preferably C.sub.2-C.sub.6 alkynyl), C.sub.5-C.sub.24 aryl (preferably C.sub.5-C.sub.14 aryl), C.sub.6-C.sub.24 alkaryl (preferably C.sub.6-C.sub.16 alkaryl), and C.sub.6-C.sub.24 aralkyl (preferably C.sub.6-C.sub.16 aralkyl).

    [0055] By functionalized as in functionalized hydrocarbyl, functionalized alkyl, functionalized olefin, functionalized cyclic olefin, and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove. The term functional group is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.

    [0056] In addition, the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above. Analogously, the above mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically mentioned above. Analogously, the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties as noted above.

    [0057] Optional or optionally means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase optionally substituted means that a non-hydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

    [0058] The term internal olefin as used herein means an olefin wherein each of the olefinic carbons (i.e., the carbons of the carbon-carbon double bond) is substituted by at least one non-hydrogen substituent. The internal olefin may be di-substituted, tri-substituted, or tetra-substituted (e.g., R.sup.1HC is CHR.sup.2; R.sup.3R.sup.4C is CHR.sup.5; R.sup.6R.sup.7C is CR.sup.8R.sup.9; where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 may be the same or different and are each independently optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl, or a functional group).

    [0059] The term terminal olefin as used herein means an olefin wherein one of the olefinic carbons (i.e., the carbons of the carbon-carbon double bond) is substituted by at least one non-hydrogen substituent and the other olefinic carbon is unsubstituted. The terminal olefin may be di-substituted or mono-substituted (e.g., CH.sub.2 is CHR.sup.10 or CH.sub.2 is CR.sup.11R.sup.12; where R.sup.10, R.sup.11, and R.sup.12 may be the same or different and are each independently optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl, or a functional group).

    [0060] The term reactant internal olefin as used herein means an internal olefin present in an olefin compound used in a cross metathesis reaction with another olefin compound to form a cross metathesis product. The reactant internal olefin may be di-substituted, tri-substituted, or tetra-substituted. The reactant internal olefin may have an E-configuration or a Z-configuration.

    [0061] The term product internal olefin as used herein means an internal olefin present in a cross metathesis product formed by a cross metathesis reaction, wherein each of the olefinic carbons (i.e., the carbons of the carbon-carbon double bond) of the internal olefin is substituted by at least one non-hydrogen substituent. The product internal olefin may be di-substituted, tri-substituted, or tetra-substituted. The product internal olefin may have an E configuration or a Z-configuration.

    [0062] The term nil, as used herein, means absent or nonexistent.

    [0063] The term hydroxyl as used herein, represents a group of formula OH.

    [0064] The term carbonyl as used herein, represents a group of formula C(O).

    [0065] The term ketone as used herein, represents an organic compound having a carbonyl group linked to a carbon atom such as C(O)R.sup.x wherein R.sup.x can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

    [0066] The term ester as used herein, represents an organic compound having a carbonyl group linked to a carbon atom such as C(O)OR wherein R.sup.x can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

    [0067] The term amine as used herein, represents a group of formula NR.sup.xR, wherein R.sup.x and R.sup.y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

    [0068] The term carboxyl as used herein, represents a group of formula C(O)O.

    [0069] The term sulfonyl as used herein, represents a group of formula SO.sub.2.

    [0070] The term sulfate as used herein, represents a group of formula OS(O).sub.2O.

    [0071] The term sulfonate as used herein, represents a group of the formula S(O).sub.2O.

    [0072] The term carboxylic acid as used herein, represents a group of formula C(O)OH.

    [0073] The term nitro as used herein, represents a group of formula NO.sub.2.

    [0074] The term cyano as used herein, represents a group of formula CN.

    [0075] The term amide as used herein, represents a group of formula C(O)NR.sup.xR.sup.y wherein R.sup.x and R.sup.y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

    [0076] The term sulfonamide as used herein, represents a group of formula S(O).sub.2NR.sup.xR.sup.y wherein R.sup.x and R.sup.y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

    [0077] The term sulfoxide as used herein, represents a group of formula S(O).

    [0078] The term phosphonic acid as used herein, represents a group of formula P(O)(OH).sub.2.

    [0079] The term phosphoric acid as used herein, represents a group of formula OP(O)(OH).sub.2.

    [0080] The term sulphonic acid as used herein, represents a group of formula S(O).sub.2OH.

    [0081] The formula H, as used herein, represents a hydrogen atom.

    [0082] The formula O, as used herein, represents an oxygen atom.

    [0083] The formula N, as used herein, represents a nitrogen atom.

    [0084] The formula S, as used herein, represents a sulfur atom.

    [0085] Functional groups may be protected in cases where the functional group interferes with the metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999). Examples of protecting groups include acetals, cyclic acetals, boronate esters (boronates), cyclic boronate esters (cyclic boronates), carbonates, or the like. Examples of protecting groups include cyclic acetals or cyclic boronate esters.

    Olefin Metathesis Catalysts

    [0086] In one embodiment, the invention provides a compound of Formula (I):

    ##STR00003##

    X is O or S;

    Y is O or S;

    Z is N or CR.SUP.32.;

    W is O, NR.SUP.33 .or S;

    [0087] R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring;
    R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring;
    R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.16 may form an optionally substituted polycyclic ring;
    R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring;
    R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.18 may form an optionally substituted polycyclic ring;
    R.sup.18 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring;
    R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl,
    R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.28 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.33 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    [0088] In another embodiment, the invention provides a catalyst represented by Formula (I) wherein:

    X is O or S;

    Y is O or S;

    Z is N or CR.SUP.32.;

    W is O, NR.SUP.33 .or S;

    [0089] R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring;
    R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring;
    R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.18 may form a polycyclic ring;
    R.sup.18 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.17 may form a polycyclic ring;
    R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl,
    R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.28 is H, optionally substituted C.sub.1-8 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.33 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    [0090] In another embodiment, the invention provides a catalyst represented by Formula (I) wherein:

    X is S;

    Y is S;

    Z is N or CR.SUP.32.;

    W is O;

    [0091] R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring;
    R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring;
    R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.16 may form an optionally substituted polycyclic ring;
    R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring;
    R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring;
    R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.17 may form an optionally substituted polycyclic ring;
    R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl,
    R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.28 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    [0092] In another embodiment, the invention provides a catalyst represented by Formula (I) wherein:

    X is S;

    Y is S;

    Z is N;

    W is O;

    [0093] R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring;
    R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring;
    R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.16 may form an optionally substituted polycyclic ring;
    R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring;
    R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.18 may form an optionally substituted polycyclic ring;
    R.sup.18 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.17 may form an optionally substituted polycyclic ring;
    R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl,
    R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.28 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    [0094] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein:

    X is S;

    Y is S;

    Z is CR.SUP.32.; W is O;

    [0095] R.sup.1 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.2 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl, optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.3 may form a polycyclic ring;
    R.sup.3 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl or together with R.sup.2 may form a polycyclic ring;
    R.sup.4 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.5 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.6 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.7 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.8 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.9 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.10 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.11 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.12 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.13 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.14 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.15 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.16 may form an optionally substituted polycyclic ring;
    R.sup.16 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.15 may form an optionally substituted polycyclic ring;
    R.sup.17 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.18 may form an optionally substituted polycyclic ring;
    R.sup.18 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl, or together with R.sup.17 may form an optionally substituted polycyclic ring;
    R.sup.19 is hydrogen, optionally substituted C.sub.1-24 alkyl, C(O)R.sup.25, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.20 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.21 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.22 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.23 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.24 is hydrogen, optionally substituted C.sub.1-24 alkyl, halogen, C(O)R.sup.25, OR.sup.26, CN, NR.sup.27R.sup.28, NO.sub.2, CF.sub.3, S(O).sub.mR.sup.29, P(O)(OH).sub.2, OP(O)(OH).sub.2, SR.sup.31, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.25 is OH, OR.sup.30, NR.sup.27R.sup.28, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl,
    R.sup.26 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.27 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.28 is H, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.29 is hydrogen, optionally substituted C.sub.1-24 alkyl, OR.sup.26, NR.sup.27R.sup.28, optionally substituted heterocycle, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.30 is optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.31 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl;
    R.sup.32 is hydrogen, optionally substituted C.sub.1-24 alkyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C.sub.5-24 aryl or optionally substituted C.sub.3-8 cycloalkenyl; and m is 1 or 2.

    [0096] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R.sup.1 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.2 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.3 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.4 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.5 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.6 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.7 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.8 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.9 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.10 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.11 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.12 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.13 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.14 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.15 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen, or together with R.sup.16 may form an optionally substituted polycyclic ring; R.sup.16 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen, or together with R.sup.15 may form an optionally substituted polycyclic ring; R.sup.17 is hydrogen, optionally substituted C.sub.1-8 alkyl, halogen, or together with R.sup.18 may form an optionally substituted polycyclic ring; R.sup.18 is hydrogen, optionally substituted C.sub.6-10 aryl, optionally substituted C.sub.1-8 alkyl, halogen, or together with R.sup.17 may form an optionally substituted polycyclic ring; R.sup.19 is optionally substituted C.sub.1-8 alkyl; R.sup.20 is hydrogen or optionally substituted C.sub.6-10 aryl; R.sup.21 is hydrogen; R.sup.22 is hydrogen; R.sup.23 is hydrogen; and R.sup.24 is hydrogen.

    [0097] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R.sup.1 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.2 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.3 is hydrogen; R.sup.4 is hydrogen; R.sup.5 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.6 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.7 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.8 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.9 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.10 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.11 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.12 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.13 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.14 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.15 is hydrogen or halogen; R.sup.16 is hydrogen; R.sup.17 is hydrogen or together with R.sup.18 may form a polycyclic ring; R.sup.18 is optionally substituted C.sub.6-10 aryl, halogen or together with R.sup.17 may form a polycyclic ring; R.sup.19 is optionally substituted C.sub.1-8 alkyl; R.sup.20 is hydrogen or optionally substituted C.sub.6-10 aryl; R.sup.21 is hydrogen; R.sup.22 is hydrogen; R.sup.23 is hydrogen; and R.sup.24 is hydrogen.

    [0098] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R.sup.1 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.2 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.3 is hydrogen; R.sup.4 is hydrogen; R.sup.5 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.6 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.7 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.8 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.9 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.10 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.11 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.12 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.13 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.14 is hydrogen, optionally substituted C.sub.1-8 alkyl or halogen; R.sup.15 is hydrogen or halogen, or together with R.sup.16 may form an optionally substituted polycyclic ring; R.sup.16 is hydrogen, or together with R.sup.15 may form an optionally substituted polycyclic ring; R.sup.17 is hydrogen or together with R.sup.18 may form an optionally substituted polycyclic ring; R.sup.18 is optionally substituted C.sub.6-10 aryl, halogen or together with R.sup.17 may form an optionally substituted polycyclic ring; R.sup.19 is optionally substituted C.sub.1-8 alkyl; R.sup.20 is hydrogen or optionally substituted C.sub.6-10 aryl; R.sup.21 is hydrogen; R.sup.22 is hydrogen; R.sup.23 is hydrogen; and R.sup.24 is hydrogen.

    [0099] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R.sup.1 is hydrogen; R.sup.2 is hydrogen; R.sup.3 is hydrogen; R.sup.4 is hydrogen; R.sup.5 is hydrogen, halogen or optionally substituted C.sub.1-8 alkyl; R.sup.6 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.7 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.8 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.9 is hydrogen, halogen or optionally substituted C.sub.1-8 alkyl; R.sup.10 is hydrogen, halogen or optionally substituted C.sub.1-8 alkyl; R.sup.11 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.12 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.13 is hydrogen or optionally substituted C.sub.1-8 alkyl; R.sup.14 is hydrogen, halogen or optionally substituted C.sub.1-8 alkyl; R.sup.15 is hydrogen or halogen, or together with R.sup.16 may form an optionally substituted polycyclic ring; R.sup.16 is hydrogen, or together with R.sup.15 may form an optionally substituted polycyclic ring; R.sup.17 is hydrogen or together with R.sup.18 may form an optionally substituted polycyclic ring; R.sup.18 is optionally substituted C.sub.6-10 aryl, halogen, or together with R.sup.17 may form an optionally substituted polycyclic ring; R.sup.19 is optionally substituted C.sub.1-8 alkyl; R.sup.20 is hydrogen or optionally substituted C.sub.6-10 aryl; R.sup.21 is hydrogen; R.sup.22 is hydrogen; R.sup.23 is hydrogen; and R.sup.24 is hydrogen.

    [0100] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R.sup.1 is optionally substituted C.sub.1-8 alkyl; R.sup.2 is optionally substituted C.sub.1-8 alkyl; R.sup.3 is hydrogen; R.sup.4 is hydrogen; R.sup.5 is halogen; R.sup.6 is hydrogen; R.sup.7 is halogen; R.sup.8 is hydrogen; R.sup.9 is halogen; R.sup.10 is halogen; R.sup.11 is hydrogen; R.sup.12 is hydrogen or halogen; R.sup.13 is hydrogen; R.sup.14 is halogen; R.sup.15 is halogen; R.sup.16 is hydrogen; R.sup.17 is hydrogen or together with R.sup.18 forms an optionally substituted naphtyl or phenantryl ring; R.sup.18 is halogen or together with R.sup.17 forms an optionally substituted naphtyl or phenantryl ring; R.sup.19 is optionally substituted C.sub.1-8 alkyl; R.sup.20 is hydrogen; R.sup.21 is hydrogen; R.sup.22 is hydrogen; R.sup.23 is hydrogen; and R.sup.24 is hydrogen.

    [0101] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R.sup.1 is hydrogen; R.sup.2 is hydrogen; R.sup.3 is hydrogen; R.sup.4 is hydrogen; R.sup.5 is hydrogen, F, methyl or i-Pr; R.sup.6 is hydrogen or t-Bu; R.sup.7 is hydrogen or methyl; R.sup.8 is hydrogen or t-Bu; R.sup.9 is hydrogen, F, methyl or i-Pr; R.sup.10 is hydrogen, F, methyl or i-Pr; R.sup.11 is hydrogen or t-Bu; R.sup.12 is hydrogen or methyl; R.sup.13 is hydrogen or t-Bu; R.sup.14 is F, methyl, i-Pr or hydrogen; R.sup.15 is hydrogen, methyl or Cl, or together with R.sup.16 forms 2-phenyl-naphthyl or phenanthryl; R.sup.16 is hydrogen, or together with R.sup.15 forms 2-phenyl-naphthyl or phenanthryl; R.sup.17 is hydrogen or together with R.sup.18 forms 2-phenyl-naphthyl, phenanthryl, or methylphenantryl; R.sup.18 is Cl, 3,5-dichloro-phenyl, phenyl, t-Bu or together with R.sup.17 forms 2-phenyl-naphthyl, phenanthryl or methylphenantryl; R.sup.19 is i-Pr; R.sup.20 is hydrogen or phenyl; R.sup.21 is hydrogen; R.sup.22 is hydrogen; R.sup.23 is hydrogen; and R.sup.24 is hydrogen.

    [0102] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R.sup.1 is methyl; R.sup.2 is methyl; R.sup.3 is hydrogen; R.sup.4 is hydrogen; R.sup.5 is F; R.sup.6 is hydrogen; R.sup.7 is hydrogen or F; R.sup.8 is hydrogen; R.sup.9 is F; R.sup.10 is F; R.sup.11 is hydrogen; R.sup.12 is hydrogen or F; R.sup.13 is hydrogen; R.sup.14 is F; R.sup.15 is Cl; R.sup.16 is hydrogen; R.sup.17 is hydrogen or together with R.sup.18 forms naphtyl or phenanthryl; R.sup.18 is hydrogen, Cl, or together with R.sup.17 forms naphtyl or phenanthryl; R.sup.19 is i-Pr; R.sup.20 is hydrogen; R.sup.21 is hydrogen; R.sup.22 is hydrogen; R.sup.23 is hydrogen; and R.sup.24 is hydrogen.

    [0103] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R.sup.1 is Me; R.sup.2 is Me; R.sup.3 is hydrogen; R.sup.4 is hydrogen; R.sup.5 is Me or F; R.sup.6 is hydrogen; R.sup.7 is hydrogen or F; R.sup.8 is hydrogen; R.sup.9 is hydrogen or F; R.sup.10 is Me or F; R.sup.11 is hydrogen; R.sup.12 is hydrogen or F; R.sup.13 is hydrogen; R.sup.14 is hydrogen or F; R.sup.15 is hydrogen or Cl; R.sup.16 is hydrogen; R.sup.17 is hydrogen or together with R.sup.18 forms naphthyl or phenantryl; R.sup.18 is Cl, phenyl or together with R.sup.17 forms naphthyl or phenantryl; R.sup.19 is i-Pr; R.sup.20 is hydrogen; R.sup.21 is hydrogen; R.sup.22 is hydrogen; R.sup.23 is hydrogen; and R.sup.24 is hydrogen.

    [0104] In one embodiment, the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R.sup.1 is hydrogen; R.sup.2 is hydrogen; R.sup.3 is hydrogen; R.sup.4 is hydrogen; R.sup.5 is Me, F or i-Pr; R.sup.6 is hydrogen or t-Bu; R.sup.7 is hydrogen or Me; R.sup.8 is hydrogen or t-Bu; R.sup.9 is hydrogen, Me, t-Bu, F or i-Pr; R.sup.10 is hydrogen, Me, F or i-Pr; R.sup.11 is hydrogen or t-Bu; R.sup.12 is hydrogen or Me; R.sup.13 is hydrogen or t-Bu; R.sup.14 is hydrogen, Me, F or i-Pr; R.sup.15 is hydrogen, methyl or Cl, or together with R.sup.16 forms 2-phenyl-naphthyl or phenanthryl; R.sup.16 is hydrogen, or together with R.sup.15 forms 2-phenyl-naphthyl or phenanthryl; R.sup.17 is hydrogen or together with R.sup.18 forms 2-phenyl-naphthyl, naphtyl, phenanthryl, or methylphenantryl; R.sup.18 is Cl, 3,5-dichloro-phenyl, phenyl, t-Bu or together with R.sup.17 forms 2-phenyl-naphthyl, naphtyl, phenanthryl or methylphenantryl; R.sup.15 is hydrogen or Cl; R.sup.16 is hydrogen; R.sup.17 is hydrogen or together with R.sup.18 form an optionally substituted naphthyl or an optionally substituted phenanthryl ring; R.sup.18 is Cl, phenyl or together with R.sup.17 form an optionally substituted naphthyl or an optionally substituted phenanthryl ring; R.sup.19 is i-Pr; R.sup.20 is hydrogen is phenyl; R.sup.21 is hydrogen; R.sup.22 is hydrogen; R.sup.23 is hydrogen; and R.sup.24 is hydrogen.

    [0105] In one embodiment, the invention provides a compound wherein the moiety

    ##STR00004##

    of Formula (I) is

    [0106] ##STR00005## ##STR00006##

    [0107] In one embodiment, the invention provides a compound wherein the moiety

    ##STR00007##

    of Formula (I) is

    [0108] ##STR00008##

    [0109] In one embodiment, the invention provides a compound wherein the moiety

    ##STR00009##

    of Formula (I) is

    [0110] ##STR00010## ##STR00011##

    [0111] In one embodiment, the invention provides a compound of Formula (I) is selected from:

    ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025##

    [0112] In one embodiment, a compound of Formula (I) is an olefin metathesis catalyst. In one embodiment, a compound of Formula (I) is a Z-selective olefin metathesis catalyst.

    [0113] In one embodiment, a compound of Formula (I) is an olefin metathesis catalyst. In one embodiment, a compound of Formula (I) is an E-selective olefin metathesis catalyst.

    Olefin Reactants

    [0114] In one embodiment, an olefin reactant comprises a reactant internal olefin, wherein the reactant internal olefin is in a Z-configuration.

    [0115] In one embodiment, an olefin reactant comprises a reactant internal olefin, wherein the reactant internal olefin is di-substituted and is in a Z-configuration.

    [0116] In one embodiment, an olefin reactant comprising a reactant internal olefin is represented by the structure of Formula (1):

    ##STR00026##

    wherein,

    [0117] D.sup.1 and D.sup.2 are identical or are independently selected from nil, CH.sub.2, O, or S; and

    [0118] E.sup.1 and E.sup.2 are identical or are independently selected from hydrogen, hydrocarbyl (e.g., C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), substituted hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl) and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (Fn) such as halo, hydroxyl, sulfhydryl, C.sub.1-C.sub.24 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.24 aralkyloxy, C.sub.6-C.sub.24 alkaryloxy, acyl (including C.sub.2-C.sub.24 alkylcarbonyl (CO-alkyl) and C.sub.6-C.sub.24 arylcarbonyl (CO-aryl)), acyloxy (O-acyl, including C.sub.2-C.sub.24 alkylcarbonyloxy (OCO-alkyl) and C.sub.6-C.sub.24 arylcarbonyloxy (OCO-aryl)), C.sub.2-C.sub.24 alkoxycarbonyl ((CO)O-alkyl), C.sub.6-C.sub.24 aryloxycarbonyl((CO)O-aryl), halocarbonyl (CO)X where X is halo), C.sub.2-C.sub.24 alkylcarbonato (O(CO)O-alkyl), C.sub.6-C.sub.24 arylcarbonato (O(CO)O-aryl), carboxy (COOH), carboxylato (COO.sup.), carbamoyl ((CO)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 haloalkyl)), di-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 haloalkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.5-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), thiocarbamoyl ((CS)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.5-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), carbamido (NH(CO)NH.sub.2), cyano (CN), cyanato (OCN), thiocyanato (SCN), isocyanate (NisCisO), thioisocyanate (NisCisS), formyl ((CO)H), thioformyl ((CS)H), amino (NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted amino (NH(C.sub.1-C.sub.24 alkyl), di-(C.sub.1-C.sub.24 alkyl)-substituted amino (N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted amino (NH(C.sub.5-C.sub.24 aryl), di-(C.sub.5-C.sub.24 aryl)-substituted amino (N(C.sub.5-C.sub.24 aryl).sub.2), C.sub.2-C.sub.24 alkylamido (NH(CO)-alkyl), C.sub.6-C.sub.24 arylamido (NH(CO)-aryl), imino (CRisNH where R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), C.sub.2-C.sub.20 alkylimino (CRisN(alkyl), where R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), arylimino (CRisN(aryl), where R includes without limitation hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), nitro (NO.sub.2), nitroso (NO), sulfo (SO.sub.2OH), sulfonato (SO.sub.2O), C.sub.1-C.sub.24 alkylsulfanyl (S-alkyl; also termed alkylthio), C.sub.5-C.sub.24 arylsulfanyl (S-aryl; also termed arylthio), C.sub.1-C.sub.24 alkylsulfinyl ((SO)-alkyl), C.sub.5-C.sub.24 arylsulfinyl ((SO)-aryl), C.sub.1-C.sub.24 alkylsulfonyl (SO.sub.2-alkyl), C.sub.1-C.sub.24 monoalkylaminosulfonyl (SO.sub.2N(H) alkyl), C.sub.1-C.sub.24 dialkylaminosulfonyl (SO.sub.2N(alkyl).sub.2), C.sub.5-C.sub.24 arylsulfonyl (SO.sub.2-aryl), boryl (BH.sub.2), borono (B(OH).sub.2), boronato (B(OR).sub.2 where R is alkyl or aryl), phosphono (P(O)(OH).sub.2), phosphonato (P(O)(O.sup.).sub.2), phosphinato (P(O)(O.sup.)), phospho (PO.sub.2), and phosphino (PH.sub.2); and the hydrocarbyl moieties C.sub.1-C.sub.24 alkyl (preferably C.sub.1-C.sub.12 alkyl, more preferably C.sub.1-C.sub.6 alkyl), C.sub.5-C.sub.24 aryl (preferably C.sub.5-C.sub.14 aryl), C.sub.6-C.sub.24 alkaryl (preferably C.sub.6-C.sub.16 alkaryl), and C.sub.6-C.sub.24 aralkyl (preferably C.sub.6-C.sub.16 aralkyl), with the proviso that if E.sup.1 is hydrogen, then D.sup.1 cannot be nil; and where if E.sup.2 is hydrogen, then D.sup.2 cannot be nil.

    [0119] In one embodiment, there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first internal olefin reactant and the second internal olefin reactant are each in a Z-configuration.

    [0120] In one embodiment, there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first olefin reactant and the second olefin reactant each comprise a reactant internal olefin.

    [0121] In one embodiment, there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first internal olefin reactant and the second internal olefin reactant each comprise a reactant internal olefin, wherein the reactant internal olefin is di-substituted and in a Z-configuration.

    [0122] In one embodiment, there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant is of Formula (1) and the second internal olefin reactant is of Formula (1), wherein the first internal olefin reactant and the second internal olefin reactant may be the same or different.

    [0123] In one embodiment, an olefin reactant comprises a reactant internal olefin, wherein the reactant internal olefin is in an E-configuration.

    [0124] In one embodiment, an olefin reactant comprises a reactant internal olefin, wherein the reactant internal olefin is di-substituted and is in an E-configuration.

    [0125] In one embodiment, an olefin reactant comprising a reactant internal olefin is represented by the structure of Formula (2):

    ##STR00027##

    wherein

    [0126] D.sup.13 and D.sup.14 are identical or are independently selected from nil, CH.sub.2, O, or S; and

    [0127] E.sup.13 and E.sup.14 are identical or are independently selected from hydrogen, hydrocarbyl (e.g., C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), substituted hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl) and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (Fn) such as halo, hydroxyl, sulfhydryl, C.sub.1-C.sub.24 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.24 aralkyloxy, C.sub.6-C.sub.24 alkaryloxy, acyl (including C.sub.2-C.sub.24 alkylcarbonyl (CO-alkyl) and C.sub.6-C.sub.24 arylcarbonyl (CO-aryl)), acyloxy (O-acyl, including C.sub.2-C.sub.24 alkylcarbonyloxy (OCO-alkyl) and C.sub.6-C.sub.24 arylcarbonyloxy (OCO-aryl)), C.sub.2-C.sub.24 alkoxycarbonyl ((CO)O-alkyl), C.sub.6-C.sub.24 aryloxycarbonyl ((CO)O-aryl), halocarbonyl (CO)X where X is halo), C.sub.2-C.sub.24 alkylcarbonato (O(CO)O-alkyl), C.sub.6-C.sub.24 arylcarbonato (O(CO)O-aryl), carboxy (COOH), carboxylato (COO.sup.), carbamoyl ((CO)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 haloalkyl)), di-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 haloalkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.5-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), thiocarbamoyl ((CS)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.5-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), carbamido (NH(CO)NH.sub.2), cyano (CN), cyanato (OCN), thiocyanato (SCN), isocyanate (NCO), thioisocyanate (NCS), formyl ((CO)H), thioformyl ((CS)H), amino (NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted amino (NH(C.sub.1-C.sub.24 alkyl), di-(C.sub.1-C.sub.24 alkyl)-substituted amino (N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted amino (NH(C.sub.5-C.sub.24 aryl), di-(C.sub.5-C.sub.24 aryl)-substituted amino (N(C.sub.5-C.sub.24 aryl).sub.2), C.sub.2-C.sub.24 alkylamido (NH(CO)-alkyl), C.sub.6-C.sub.24 arylamido (NH(CO)-aryl), imino (CRNH where R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), C.sub.2-C.sub.20 alkylimino (CRN(alkyl), where R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), arylimino (CRN(aryl), where R includes without limitation hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), nitro (NO.sub.2), nitroso (NO), sulfo (SO.sub.2OH), sulfonato (SO.sub.2O), C.sub.1-C.sub.24 alkylsulfanyl (S-alkyl; also termed alkylthio), C.sub.5-C.sub.24 arylsulfanyl (S-aryl; also termed arylthio), C.sub.1-C.sub.24 alkylsulfinyl ((SO)-alkyl), C.sub.5-C.sub.24 arylsulfinyl ((SO)-aryl), C.sub.1-C.sub.24 alkylsulfonyl (SO.sub.2-alkyl), C.sub.1-C.sub.24 monoalkylaminosulfonyl (SO.sub.2N(H) alkyl), C.sub.1-C.sub.24 dialkylaminosulfonyl (SO.sub.2N(alkyl).sub.2), C.sub.5-C.sub.24 arylsulfonyl (SO.sub.2-aryl), boryl (BH.sub.2), borono (B(OH).sub.2), boronato (B(OR).sub.2 where R is alkyl or aryl), phosphono (P(O)(OH).sub.2), phosphonato (P(O)(O.sup.).sub.2), phosphinato (P(O)(O.sup.)), phospho (PO.sub.2), and phosphino (PH.sub.2); and the hydrocarbyl moieties C.sub.1-C.sub.24 alkyl (preferably C.sub.1-C.sub.12 alkyl, more preferably C.sub.1-C.sub.6 alkyl), C.sub.5-C.sub.24 aryl (preferably C.sub.5-C.sub.14 aryl), C.sub.6-C.sub.24 alkaryl (preferably C.sub.6-C.sub.16 alkaryl), and C.sub.6-C.sub.24 aralkyl (preferably C.sub.6-C.sub.16 aralkyl).

    [0128] In one embodiment, there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first internal olefin reactant and the second internal olefin reactant are each in an E-configuration.

    [0129] In one embodiment, there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first internal olefin reactant and the second internal olefin reactant each comprise a reactant internal olefin, wherein the reactant internal olefin is di-substituted and is in an E-configuration.

    [0130] In one embodiment, there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant is of Formula (2) and the second internal olefin reactant is of Formula (2), wherein the first internal olefin reactant and the second internal olefin reactant may be the same or different.

    [0131] In general the second olefin reactant comprising a terminal olefin may be represented by the structure of Formula (3):

    ##STR00028##

    wherein U.sup. is selected from the group comprising nil, CH.sub.2, O, or S and T.sup. is selected from the group consisting of hydrogen, hydrocarbyl (e.g., C.sub.1-C.sub.2 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), substituted hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl) and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (Fn) such as phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C.sub.1-C.sub.20 alkylsulfanyl, C.sub.5-C.sub.20 arylsulfanyl, C.sub.1-C.sub.20 alkylsulfonyl, C.sub.5-C.sub.20 arylsulfonyl, C.sub.1-C.sub.20 alkylsulfinyl, C.sub.5-C.sub.20 arylsulfinyl, sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C.sub.1-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.5-C.sub.20 aryloxycarbonyl, carboxyl, carboxylato, mercapto, formyl, C.sub.1-C.sub.20 thioester, cyano, cyanato, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, or halogen, or a metal-containing or metalloid-containing group (wherein the metal may be, for example, Sn or Ge).

    [0132] In one embodiment, there is a first internal olefin reactant and a second terminal olefin reactant, wherein the first internal olefin reactant is in an E-configuration.

    [0133] In one embodiment, there is a first internal olefin reactant and a second terminal olefin reactant, wherein the first internal olefin reactant is in a Z-configuration.

    [0134] In one embodiment, there is a first internal olefin reactant and a second terminal olefin reactant, where the first internal olefin reactant is of Formula (1) and the second terminal olefin reactant is of Formula (3).

    [0135] In one embodiment, there is a first internal olefin reactant and a second terminal olefin reactant, where the first internal olefin reactant is of Formula (2) and the second terminal olefin reactant is of Formula (3).

    Olefin Products

    [0136] In one embodiment, the olefin product is at least one cross metathesis product, wherein the at least one cross metathesis product is in a Z-configuration.

    [0137] In one embodiment, the olefin product is at least one cross metathesis product, wherein the at least one cross metathesis product is di-substituted and is in a Z-configuration.

    [0138] In one embodiment, an at least one cross metathesis product comprises a product internal olefin, wherein the product internal olefin is in a Z-configuration.

    [0139] In one embodiment, an at least one cross metathesis product comprises a product internal olefin, wherein the product internal olefin is di-substituted and is in a Z-configuration.

    [0140] In one embodiment, the olefin product is at least one cross metathesis product, wherein the at least one cross metathesis product is in an E-configuration.

    [0141] In one embodiment, the olefin product is at least one cross metathesis product, wherein the at least one cross metathesis product is di-substituted and is in an E-configuration.

    [0142] In one embodiment, an at least one cross metathesis product comprises a product internal olefin, wherein the product internal olefin is in an E-configuration.

    [0143] In one embodiment, an at least one cross metathesis product comprises a product internal olefin, wherein the product internal olefin is di-substituted and is in an E-configuration.

    [0144] In some embodiments, the invention provides a method that produces a compound (i.e., a product, olefin product; e.g., cross metathesis product) having a carbon-carbon double bond (e.g., a product internal olefin) in a Z:E ratio greater than about 1:1, greater than about 2:1, greater than about 3:1, greater than about 4:1, greater than about 5:1, greater than about 6:1, greater than about 7:1, greater than about 8:1, greater than about 9:1, greater than about 95:5, greater than about 96:4, greater than about 97:3, greater than about 98:2, or in some cases, greater than about 99:1. In some cases, about 100% of the carbon-carbon double bond produced in the metathesis reaction may have a Z configuration. The Z or cis selectivity may also be expressed as a percentage of product formed (e.g., cross metathesis product). In some cases, the product (e.g., cross metathesis product) may be greater than about 50% Z, greater than about 60% Z, greater than about 70% Z, greater than about 80% Z, greater than about 90% Z, greater than about 95% Z, greater than about 96% Z, greater than about 97% Z, greater than about 98% Z, greater than about 99% Z, or in some cases greater than about 99.5% Z.

    [0145] In another embodiment, an at least one cross metathesis product comprising a product internal olefin is represented by the structure of Formula (4):

    ##STR00029##

    wherein,

    [0146] D.sup.3 and D.sup.4 are identical or are independently selected from nil, CH.sub.2, O, or S; and

    [0147] E.sup.3 and E.sup.4 are identical or are independently selected from hydrogen, hydrocarbyl (e.g., C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), substituted hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl) and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (Fn) such as halo, hydroxyl, sulfhydryl, C.sub.1-C.sub.24 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.24 aralkyloxy, C.sub.6-C.sub.24 alkaryloxy, acyl (including C.sub.2-C.sub.24 alkylcarbonyl (CO-alkyl) and C.sub.6-C.sub.24 arylcarbonyl (CO-aryl)), acyloxy (O-acyl, including C.sub.2-C.sub.24 alkylcarbonyloxy (OCO-alkyl) and C.sub.6-C.sub.24 arylcarbonyloxy (OCO-aryl)), C.sub.2-C.sub.24 alkoxycarbonyl ((CO)O-alkyl), C.sub.6-C.sub.24 aryloxycarbonyl ((CO)O-aryl), halocarbonyl (CO)X where X is halo), C.sub.2-C.sub.24 alkylcarbonato (O(CO)O-alkyl), C.sub.6-C.sub.24 arylcarbonato (O(CO)O-aryl), carboxy (COOH), carboxylato (COO.sup.), carbamoyl ((CO)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 haloalkyl)), di-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 haloalkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)NH-aryl), di-(C.sub.1-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.1-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), thiocarbamoyl ((CS)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl)(C.sub.1-C.sub.24 aryl), carbamido (NH(CO)NH.sub.2), cyano (CN), cyanato (OCN), thiocyanato (SCN), isocyanate (NisCisO), thioisocyanate (NisCisS), formyl ((CO)H), thioformyl ((CS)H), amino (NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted amino (NH(C.sub.1-C.sub.24 alkyl), di-(C.sub.1-C.sub.24 alkyl)-substituted amino (N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.1-C.sub.24 aryl)-substituted amino (NH(C.sub.1-C.sub.24 aryl), di-(C.sub.5-C.sub.24 aryl)-substituted amino (N(C.sub.5-C.sub.24 aryl).sub.2), C.sub.2-C.sub.24 alkylamido (NH(CO)-alkyl), C.sub.6-C.sub.24 arylamido (NH(CO)-aryl), imino (CRisNH where R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), C.sub.2-C.sub.20 alkylimino (CRisN(alkyl), where R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.1-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), arylimino (CRisN(aryl), where R includes without limitation hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), nitro (NO.sub.2), nitroso (NO), sulfo (SO.sub.2OH), sulfonato (SO.sub.2O), C.sub.1-C.sub.24 alkylsulfanyl (S-alkyl; also termed alkylthio), C.sub.1-C.sub.24 arylsulfanyl (S-aryl; also termed arylthio), C.sub.1-C.sub.24 alkylsulfinyl ((SO)-alkyl), C.sub.1-C.sub.24 arylsulfinyl ((SO)-aryl), C.sub.1-C.sub.24 alkylsulfonyl (SO.sub.2-alkyl), C.sub.1-C.sub.24 monoalkylaminosulfonyl(SO.sub.2N(H) alkyl), C.sub.1-C.sub.24 dialkylaminosulfonyl (SO.sub.2N(alkyl).sub.2), C.sub.1-C.sub.24 arylsulfonyl (SO.sub.2-aryl), boryl (BH.sub.2), borono (B(OH).sub.2), boronato (B(OR).sub.2 where R is alkyl or aryl), phosphono (P(O)(OH).sub.2), phosphonato (P(O)(O.sup.).sub.2), phosphinato (P(O)(O.sup.)), phospho (PO.sub.2), and phosphino (PH.sub.2); and the hydrocarbyl moieties C.sub.1-C.sub.24 alkyl (preferably C.sub.1-C.sub.12 alkyl, more preferably C.sub.1-C.sub.6 alkyl), C.sub.5-C.sub.24 aryl (preferably C.sub.5-C.sub.14 aryl), C.sub.6-C.sub.24 alkaryl (preferably C.sub.6-C.sub.16 alkaryl), and C.sub.6-C.sub.24 aralkyl (preferably C.sub.6-C.sub.16 aralkyl), with the proviso that if E.sup.3 is hydrogen, then D.sup.3 cannot be nil; and where if E.sup.4 is hydrogen, then D.sup.4 cannot be nil.

    [0148] In some embodiments, the invention provides a method that produces a compound (i.e., a product, olefin product; e.g., cross metathesis product) having a carbon-carbon double bond (e.g., a product internal olefin) in an E:Z ratio greater than about 1:1, greater than about 2:1, greater than about 3:1, greater than about 4:1, greater than about 5:1, greater than about 6:1, greater than about 7:1, greater than about 8:1, greater than about 9:1, greater than about 95:5, greater than about 96:4, greater than about 97:3, greater than about 98:2, or in some cases, greater than about 99:1. In some cases, about 100% of the carbon-carbon double bond produced in the metathesis reaction may have an E configuration. The E or trans selectivity may also be expressed as a percentage of product formed (e.g., cross metathesis product). In some cases, the product (e.g., cross metathesis product) may be greater than about 50% E, greater than about 60% E, greater than about 70% E, greater than about 80% E, greater than about 90% E, greater than about 95% E, greater than about 96% E, greater than about 97% E, greater than about 98% E, greater than about 99% E, or in some cases greater than about 99.5% E.

    [0149] In another example an at least one cross metathesis product comprising a product internal olefin, wherein the product internal olefin is in the E-configuration may be represented by the structure of Formula (5):

    ##STR00030##

    wherein, D.sup.19 and D.sup.21 are identical or are independently selected from nil, CH.sub.2, O, or S; and E.sup.19 and E.sup.21 are identical or are independently selected from hydrogen, hydrocarbyl (e.g., C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), substituted hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30 alkaryl) and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (Fn) such as halo, hydroxyl, sulfhydryl, C.sub.1-C.sub.24 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.24 aralkyloxy, C.sub.6-C.sub.24 alkaryloxy, acyl (including C.sub.2-C.sub.24 alkylcarbonyl (CO-alkyl) and C.sub.6-C.sub.24 arylcarbonyl (CO-aryl)), acyloxy (O-acyl, including C.sub.2-C.sub.24 alkylcarbonyloxy (OCO-alkyl) and C.sub.6-C.sub.24 arylcarbonyloxy (OCO-aryl)), C.sub.2-C.sub.24 alkoxycarbonyl ((CO)O-alkyl), C.sub.6-C.sub.24 aryloxycarbonyl ((CO)O-aryl), halocarbonyl (CO)X where X is halo), C.sub.2-C.sub.24 alkylcarbonato (O(CO)O-alkyl), C.sub.6-C.sub.24 arylcarbonato (O(CO)O-aryl), carboxy (COOH), carboxylato (COO.sup.), carbamoyl ((CO)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 haloalkyl)), di-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 haloalkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.5-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), thiocarbamoyl ((CS)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.5-C.sub.24 aryl).sub.2), di-N(C.sub.1-C.sub.24 alkyl), N(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl), carbamido (NH(CO)NH.sub.2), cyano (CN), cyanato (OC), thiocyanato (SCN), isocyanate (NCO), thioisocyanate (NCS), formyl ((CO)H), thioformyl ((CS)H), amino (NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted amino (NH(C.sub.1-C.sub.24 alkyl), di-(C.sub.1-C.sub.24 alkyl)-substituted amino (N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted amino (NH(C.sub.5-C.sub.24 aryl), di-(C.sub.5-C.sub.24 aryl)-substituted amino (N(C.sub.5-C.sub.24 aryl).sub.2), C.sub.2-C.sub.24 alkylamido (NH(CO)-alkyl), C.sub.6-C.sub.24 arylamido (NH(CO)-aryl), imino (CRNH where R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), C.sub.2-C.sub.20 alkylimino (CRN(alkyl), where R includes without limitation hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), arylimino (CRN(aryl), where R includes without limitation hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), nitro (NO.sub.2), nitroso (NO), sulfo (SO.sub.2OH), sulfonato (SO.sub.2O), C.sub.1-C.sub.24 alkylsulfanyl (S-alkyl; also termed alkylthio), C.sub.5-C.sub.24 arylsulfanyl (S-aryl; also termed arylthio), C.sub.1-C.sub.24 alkylsulfinyl ((SO)-alkyl), C.sub.5-C.sub.24 arylsulfinyl ((SO)-aryl), C.sub.1-C.sub.24 alkylsulfonyl (SO.sub.2-alkyl), C.sub.1-C.sub.24 monoalkylaminosulfonyl(SO.sub.2N(H) alkyl), C.sub.1-C.sub.24 dialkylaminosulfonyl (SO.sub.2N(alkyl).sub.2), C.sub.5-C.sub.24 arylsulfonyl (SO.sub.2-aryl), boryl (BH.sub.2), borono (B(OH).sub.2), boronato (B(OR).sub.2 where R is alkyl or aryl), phosphono (P(O)(OH).sub.2), phosphonato (P(O)(O.sup.).sub.2), phosphinato (P(O)(O.sup.)), phospho (PO.sub.2), and phosphino (PH.sub.2); and the hydrocarbyl moieties C.sub.1-C.sub.24 alkyl (preferably C.sub.1-C.sub.12 alkyl, more preferably C.sub.1-C.sub.6 alkyl), C.sub.5-C.sub.24 aryl (preferably C.sub.5-C.sub.14 aryl), C.sub.6-C.sub.24 alkaryl (preferably C.sub.6-C.sub.16 alkaryl), and C.sub.6-C.sub.24 aralkyl (preferably C.sub.6-C.sub.16 aralkyl); with the proviso that if E.sup.21 is hydrogen, then D.sup.21 cannot be nil; and where if E.sup.19 is hydrogen, then D.sup.19 cannot be nil.

    EXPERIMENTAL

    [0150] In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental error and deviation should be accounted for. Unless indicated otherwise, temperature is in degrees Celsius and pressure is at or near atmospheric. The examples are to be considered as not being limiting of the invention as described herein and are instead provided as representative examples of the catalyst compounds of the invention, of the methods that may be used in their preparation, and of the methods of using the inventive catalysts.

    [0151] All manipulations were carried out under an inert atmosphere using an argon-filled glovebox or standard Schlenk techniques. All glassware was oven dried prior to use. All solvents were anhydrous grade and sparged with argon before use. All reagents, unless specified, were obtained from commercial sources and used without further purification. Other reagents, including catalysts C711, C767, C643, C627 and C823 were prepared according to previously reported literature procedures. Trans-methyl-9-octadecenoate (>97%) and Cis-methyl-9-octadecenoate (>99%) were purchased from TCI.

    [0152] .sup.1HNMR spectra were obtained at 400 MHz respectively. .sup.1H were recorded relative to residual protio-solvent.

    [0153] GC Methods: Volatile products were analyzed using an Agilent 6850 gas chromatography (GC) instrument with a flame ionization detector (FID). The following conditions and equipment were used:

    Method 1: Column: DB-225, 30 m0.25 mm (ID)0.25 m film thickness.

    Manufacturer: Agilent

    [0154] GC and column conditions: Injector temperature: 220 C., Detector temperature: 220 C.
    Oven temperature: Starting temperature: 35 C., hold time: 0.5 minutes. [0155] Ramp rate 10 C./min to 130 C., hold time: 0 minutes. [0156] Ramp rate 20 C./min to 220 C., hold time: 5 minutes.

    Carrier gas: Helium

    [0157] Mean gas velocity: 25 cm/sec
    Split ratio: 20:1
    Method 2: Column: HP-5, 30 m0.25 mm (ID)0.25 m film thickness.

    Manufacturer: Agilent

    [0158] GC and column conditions: Injector temperature: 250 C., Detector temperature: 280 C.
    Oven temperature: Starting temperature: 100 C., hold time: 1 minute [0159] Ramp rate 10 C./min to 270 C., hold time: 12 minutes.

    Carrier gas: Helium

    [0160] Average velocity: 30 cm/sec
    Split ratio: 40.8:1

    [0161] The following abbreviations are used herein:

    TABLE-US-00001 RT or r.t. room termperature mL milliliter L microliter CD.sub.2Cl.sub.2 deuterated dichloromethane C. degrees Celsius h hour g gram mg milligram THF tetrahydrofuran THF-d.sub.8 deuterated tetrahydrofuran DMSO-d.sub.6 deuterated dimethylsulfoxide iPr isopropyl (CH(CH.sub.3).sub.2) Zn(OAc).sub.22 H.sub.2O zinc acetate dehydrate HC(OEt).sub.3 triethyl orthoformate HCl hydrochloric acid PhCl chlorobenzene NaBF.sub.4 sodium tetrafluoroborate NaOtBu sodium tert-butoxide NaOH sodium hydride LiAlH.sub.4 lithium aluminum hydride KHMDS potassium bis(trimethylsilyl)amide [00031]embedded image 3-bromo-2-methylpropene

    Example 1

    Preparation of (3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II)

    [0162] ##STR00032##

    [0163] To a 250 mL round bottom flask equipped with a magnetic stir bar was added 3,6-dichlorobenzene-1,2-dithiol (2.00 g, 9.47 mmol), Zn(OAc).sub.2.2 H.sub.2O (8.32 g, 37.9 mmol), ethylenediamine (3.80 mL, 56.8 mmol), and isopropanol (100 mL). The resulting suspension was rapidly stirred for 24 h at room temperature. The resulting precipitate was isolated by filtration, washed with methanol (50 mL), hot chloroform (50 mL), then dried under vacuum overnight affording (3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) as an light yellow solid (2.78 g, 87.9%).

    [0164] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 6.78 (br s, 2H), 4.06 (br s, 4H), 2.65 (br s, 4H).

    Example 2

    General Procedure for the Preparation of a Compound of Formula (I): C849z

    [0165] ##STR00033##

    [0166] In an argon filled glovebox, a 40 mL scintillation vial equipped with a magnetic stir bar was charged with C711 (0.500 g, 0.703 mmol), (3,6-dichlorobenzene-1,2-dithiolato) (ethylenediamine)zinc(II) (259 mg, 0.774 mmol), and 15 mL THF. The resulting suspension was stirred for 6 h at room temperature then devolatilized. The resulting residue was dissolved in a minimal amount of dichloromethane, filtered through a pad of celite, recrystallized from dichloromethane/diethyl ether at 30 C. The red/brown crystals were isolated by filtration and dried under vacuum to afford C849z (462 mg, 77.4%).

    [0167] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) 14.52 (s, 1H), 7.52-7.34 (m, 4H), 7.31 (d, J=6.8 Hz, 1H), 7.20 (d, J=6.4 Hz, 1H), 6.86-6.97 (m, 2H), 6.82 (t, J i=7.3 Hz, 2H), 6.74 (d, J=7.0 Hz, 1H), 6.55 (d, J=6.3 Hz, 1H), 4.97 (hept, J=5.6 Hz, 1H), 4.36 (dd, J=20.2, 10.5 Hz, 1H), 4.18 (dd, J=19.1, 9.4 Hz, 1H), 4.02 (dd, J=17.6, 9.5 Hz, 1H), 3.96-3.80 (m, 3H), 3.21-2.99 (m, 1H), 2.54-2.34 (m, 1H), 1.91 (d, J=5.5 Hz, 3H), 1.43 (d, J=5.8 Hz, 3H), 1.38 (d, J=5.9 Hz, 3H), 1.20-1.35 (m, 6H), 1.00-1.10 (m, 6H), 0.94 (d, J=5.9 Hz, 3H), 0.54 (d, J=5.6 Hz, 3H), 0.04 (d, J=5.4 Hz, 3H).

    Example 3

    Preparation of C905

    [0168] ##STR00034##

    [0169] In an argon filled glovebox, a 40 mL scintillation vial equipped with a magnetic stir bar was charged with C767 (0.150 g, 0.196 mmol), (3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.072 g, 0.22 mmol), and tetrahydrofuran (10 mL). The resulting suspension was stirred for 1 hour at ambient temperature then devolatilized. The residue was dissolved in dichloromethane (10 mL), filtered through a pad of celite, diluted with hexanes (10 mL) then concentrated under vacuum. Reducing the volume to 5 mL afforded a yellow/brown microcrystalline solid which was isolated by filtration, washed with cold hexanes (23 mL) and dried under vacuum to afford C905 (0.142 g, 80.4%).

    [0170] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) 14.39 (s, 1H), 7.66 (br s, 1H), 7.55 (d, J=1.7 Hz, 2H), 7.44 (t, J=1.8 Hz, 1H), 7.38-7.30 (m, 2H), 6.96 (d, J=8.7 Hz, 1H), 6.94 (d, J=8.1 Hz, 1H), 6.86 (d, J=8.1 Hz, 1H), 6.76 (t, J=7.4 Hz, 1H), 6.56 (dd, J=7.5, 1.5 Hz, 1H), 6.26 (br s, 1H), 5.05 (septet, J=6.3 Hz, 1H), 4.49-4.38 (m, 1H), 4.08-3.97 (m, 3H), 1.59 (br s, 9H), 1.28 (d, J=6.2 Hz, 3H), 1.15 (s, 18H), 1.06 (br s, 9H), 1.02 (d, J=6.4 Hz, 3H).

    Example 4

    Preparation of C765

    [0171] ##STR00035##

    [0172] C765 was synthesized according to the procedure described in US 2014/0371454. C765 was isolated as red/brown crystals in 97.1% yield.

    Example 5

    Preparation of N.SUP.1.,N.SUP.2.-bis(2-fluoro-6-methylphenyl)oxalamide

    [0173] ##STR00036##

    [0174] To a 500 mL round bottom flask equipped with a magnetic stir bar was added 2-methyl-6-fluoroaniline (15.0 mL, 130 mmol), tetrahydrofuran/water (1:1, 200 mL), NaOH (5.19 g, 130 mmol), and triethylamine (0.90 mL, 6.5 mmol). The suspension was stirred vigorously at 0 C. and oxalyl chloride (6.58 mL, 77.8 mmol) was added dropwise. After complete addition, the reaction was stirred for 1 hour while warming to ambient temperature. The resulting solid was isolated by filtration, washed with 1M HCl (50 mL), water (350 mL), and diethyl ether (250 mL) then dried under vacuum to afford N.sup.1,N.sup.2-bis(2-fluoro-6-methylphenyl)oxalamide (7.05 g, 35.7% yield). .sup.1H NMR (400 MHz, DMSO-d.sub.6) 10.52 (s, 1H), 7.32-7.24 (m, 2H), 7.19-7.11 (m, 4H), 2.24 (s, 6H).

    Example 6

    Preparation of 1,3-bis(2-fluoro-6-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride

    [0175] ##STR00037##

    [0176] In an argon filled glovebox, lithium aluminum hydride (3.74 g, 98.6 mmol) and tetrahydrofuran/toluene (1:1, 100 mL) were combined in a 500 mL round bottom flask equipped with a magnetic stir bar. N.sup.1,N.sup.2-bis(2-fluoro-6-methylphenyl)oxalamide (6.00 g, 19.7 mmol) was subsequently added to the suspension in small portions with stirring. The reaction vessel was sealed, removed from the glovebox, fitted with a reflux condenser and heated to 50 C. under argon for 12 h. After cooling to ambient temperature the reaction was quenched by slowly adding water (3.8 mL), followed by aqueous sodium hydroxide (15 wt %, 3.8 mL), then an additional portion of water (11.4 mL). The reaction was stirred rapidly for 2 hours then decanted away from solid residues and dried over magnesium sulfate. Filtration through a pad of celite afforded a clear solution which was combined with hydrochloric acid (2.0 M in ether, 30 mL, 60 mmol). The resulting precipitate was isolated by filtration then combined with triethyl orthoformate (30 mL) and heated to 130 C. for 1 hour. After cooling the reaction to ambient temperature, the precipitate was isolated by filtration, washed with diethyl ether (225 mL), hexanes (250 mL), then dried under vacuum to afford 1,3-bis(2-fluoro-6-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride (4.56 g, 71.7% yield).

    [0177] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.63 (s, 1H), 7.55-7.47 (m, 2H), 7.38 (t, J=9.2 Hz, 2H), 7.31 (d, J=7.8 Hz, 2H), 4.57 (s, 4H), 2.48 (s, 6H).

    Example 7

    Preparation of C829

    [0178] ##STR00038##

    [0179] In an argon filled glovebox, C823 (0.676 g, 0.822 mmol), 1,3-bis(2-fluoro-6-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride (0.500 g, 1.64 mmol) and toluene (50 mL) were combined in a 250 mL round bottom flask equipped with a magnetic stir bar. A solution of potassium bis(trimethylsilyl)amide (0.328 g, 1.64 mmol) in toluene (20 mL) was subsequently added and the solution stirred at ambient temperature for 2 hours. All volatiles were subsequently removed in vacuum. The resulting residue was dissolved in dichloromethane (10 mL), filtered through a pad of celite, and devolatilized. The crude product was triturated with hexanes (220 mL) then recrystallized from toluene/hexanes at ambient temperature. The crystalline complex was isolated by filtration and dried under vacuum to afford C829 (0.454 g, 66.7% yield).

    [0180] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) 19.28 (s, 1H), 9.4-8.0 (br s 1H), 7.41-7.30 (m, 2H). 7.20 (d, J=7.6 Hz, 1H), 7.16-7.04 (m, 3H), 6.90-5.80 (br s, 3H), 6.72-6.62 (m, 1H), 4.22-3.75 (m, 4H), 2.75 (pseudo d, J=16.5 Hz, 3H), 2.55-2.05 (br s, 3H), 2.11 (pseudo dd, J=22.7, 11.9 Hz, 3H), 1.65-1.23 (m, 15H), 1.10-0.72 (m, 15H)

    Example 8

    Preparation of C745

    [0181] ##STR00039##

    [0182] In an argon filled glovebox, C829 (0.300 g, 0.362 mmol), 1-isopropoxy-2-(prop-1-en-1-yl)benzene (0.638 g, 3.62 mmol) and toluene (10 mL) were combined in a 40 mL scintillation vial equipped with a magnetic stir bar. The reaction was stirred at ambient temperature for 14 hours then directly adsorbed onto silica gel. Purification by column chromatography (silica gel, 2 to 6% gradient of ethyl acetate/hexanes) afforded 0.190 g (90% pure) of crude intermediate. The crude intermediate was subsequently combined with (3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.115 g, 0.345 mmol) and tetrahydrofuran (5 mL) in a 20 mL scintillation vial equipped with a magnetic stir bar. After 4 hours of stirring at ambient temperature, all volatiles were removed, the residue dissolved in dichloromethane, filtered through celite, devolatilized and recrystallized from dichloromethane/diethyl ether at 35 C. The resulting yellow/brown crystals were isolated by filtration, washed with cold diethyl ether (25 mL) then dried under vacuum to afford C745 (0.116 g, 35.7% yield).

    [0183] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) [three conformers in solution, 8:25:67] 14.42 (s, 0.08H), 14.39 (s, 0.25H), 14.36 (s, 0.67H), 7.37-7.27 (m, 1H), 7.26-7.02 (m, 2.7H), 7.02-6.62 (m, 7.3H), 6.41 (s, 0.4H), 6.10 (t, J=9.0 Hz, 0.6H), 5.47-5.38 (m, 1H), 4.13-3.86 (m, 4H), 2.61-2.40 (m, 5H), 1.85-1.65 (m, 7H).

    Example 9

    Preparation of N,N-bis(2,6-difluorophenyl)formimidamide

    [0184] ##STR00040##

    [0185] To a 100 mL round bottom flask equipped with a magnetic stir bar was added 2,6-difluoroaniline (10.0 mL, 95.9 mmol) and triethyl orthoformate (8.11 mL, 48.8 mmol). To the stirring solution was added hydrochloric acid (0.040 mL, 12 M, 0.48 mmol) and the reaction stirred at ambient temperature for 10 minutes. The reaction solidified and was subsequently sonicated for an additional 10 minutes. The resulting precipitate was subsequently isolated by filtration, washed with hexanes (230 mL) then dried under vacuum to afford N,N-bis(2,6-difluorophenyl)formimidamide (8.47 g, 67.9% yield).

    [0186] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.47 (br s, 1H), 8.03 (s, 1H), 7.10 (br s, 6H).

    Example 10

    Preparation of 1,3-bis(2,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-ium tetrafluoroborate

    [0187] ##STR00041##

    [0188] To a 20 mL scintillation vial equipped with a magnetic stir bar was added N,N-bis(2,6-difluorophenyl)formimidamide (4.00 g, 14.9 mmol), 3-bromo-2-methylpropene (1.65 mL, 16.4 mmol), and chlorobenzene (120 mL). The reaction was heated to 125 C. for 24 h. After cooling the resulting precipitate was isolated by filtration and washed with diethyl ether (220 mL). The crude product was then partitioned between dichloromethane and an aqueous sodium tetrafluoroborate solution (100 mL, 1:1, 2.0 g NaBF.sub.4/50 mL). The organic layer was separated, dried over magnesium sulfate, filtered through celite and all volatiles were removed by rotary evaporation. The resulting reside was recrystallized from dichloromethane/diethyl ether to afford 1,3-bis(2,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-ium tetrafluoroborate (3.25 g, 53.1% yield).

    [0189] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.59 (s, 1H), 7.79 (m, 1H), 7.70-7.60 (m, 1H), 7.55-7.42 (m, 4H), 4.55 (s, 2H), 1.54 (s, 6H).

    Example 11

    Preparation of C642

    [0190] ##STR00042##

    [0191] In an argon filled glovebox, 1,3-bis(2,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-ium tetrafluoroborate (0.500 g, 1.22 mmol), NaOtBu (0.117 g, 1.22 mmol), and C823 (0.502 g, 0.610 mmol) were weighed into separate 40 mL scintillation vials equipped with magnetic stir bars and each dissolved/suspended in tetrahydrofuran (10 mL). The solutions/suspensions were cooled to 35 C. then the solution of NaOtBu was added to the solution of 1,3-bis(2,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-ium tetrafluoroborate over 2 minutes. The reaction was stirred at 35 C. for 1 h then combined with the chilled suspension of C823 and stirred for an additional hour at 35 C. before allowing the reaction to slowly warm to ambient temperature overnight. The reaction was subsequently devolatilized, triturated with hexanes (240 mL), dissolved in toluene (10 mL), and filtered through celite. The crude solution was combined with a solution of 1-isopropoxy-2-(prop-1-en-1-yl)benzene (0.400 g, 2.27 mmol) in toluene (2 mL) and stirred overnight at ambient temperature. The resulting green precipitate was isolated by filtration, washed with toluene/hexanes (1:3, 210 mL) then dried under vacuum to afford C642 (0.221 g, 56.4% yield).

    [0192] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) 16.76 (s, 1H), 7.59-7.54 (m, 1H), 7.53-7.41 (m, 2H), 7.17-7.07 (m, 5H), 6.98-6.90 (m, 2H), 5.07-4.96 (sept, J=6.2 Hz, 1H), 4.06 (s, 2H), 1.49 (s, 3H), 1.48 (s, 3H), 1.42 (d, J=6.1 Hz, 6H).

    Example 12

    Preparation of C781

    [0193] ##STR00043##

    [0194] In an argon filled glovebox, C642 (0.150 g, 0.234 mmol) and (3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.086 g, 0.26 mmol) were combined in a 20 mL scintillation vial equipped with a magnetic stir bar and dissolved in tetrahydrofuran (10 mL). The reaction was stirred for 60 minutes then devolatilized, dissolved in dichloromethane, filtered, and recrystallized from dichloromethane/diethyl ether at 35 C. The resulting yellow/brown crystals were washed with cold diethyl ether (23 mL) then dried under vacuum to afford C781 (0.128 g, 70.2% yield).

    [0195] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) [two conformers in solution, 40:60] 14.52 br s (0.4H), 14.43 (br s, 0.6H), 7.33 (t, J=7.4 Hz, 1H), 7.08 (d, J=8.4 Hz, 1H), 7.05-6.67 (m, 9H), 6.13 (br s, 1H), 5.42 (br s, 1H), 3.94 (br q, J=8.0 Hz, 1.2H), 3.78 (br s, 0.8H), 1.88-1.74 (m, 6H), 1.50-1.28 (m, 6H).

    Example 13

    Preparation of N,N-bis(2,4,6-trifluorophenyl)formimidamide

    [0196] ##STR00044##

    [0197] To a 100 mL round bottom flask equipped with a magnetic stir bar was added 2,4,6-difluoroaniline (10.0 g, 68.0 mmol), hexanes (25 mL), and triethyl orthoformate (5.94 mL, 35.7 mmol). To the stirring solution was added hydrochloric acid (0.180 mL, 2 M in diethyl ether, 0.36 mmol) and the reaction stirred at ambient temperature for 60 minutes. The resulting precipitate was subsequently isolated by filtration, washed with hexanes (210 mL) then dried under vacuum to afford N,N-bis(2,4,6-difluorophenyl)formimidamide (7.73 g, 74.8% yield).

    [0198] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.27 (br s, 1H), 7.98 (s, 1H), 7.19 (br s, 4H).

    Example 14

    Preparation of 1,3-bis(2,4,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-ium tetrafluoroborate

    [0199] ##STR00045##

    [0200] To a 40 mL scintillation vial equipped with a magnetic stir bar was added N,N-bis(2,4,6-trifluorophenyl)formimidamide (0.511 g, 1.68 mmol), 3-bromo-2-methylpropene (0.200 mL, 1.97 mmol), and ortho-dichlorobenzene (4 mL). The reaction was heated to 120 C. for 60 h. After cooling to 0 C. the resulting precipitate was isolated by filtration and washed with hexanes (315 mL). The crude product was then partitioned between dichloromethane and an aqueous sodium tetrafluoroborate solution (30 mL, 1:1, 0.75 g NaBF.sub.4/15 mL). The organic layer was separated and all volatiles were removed by rotary evaporation affording 1,3-bis(2,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-ium tetrafluoroborate (0.339 g, 45.2% yield).

    [0201] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.49 (s, 1H), 7.71-7.59 (m, 4H), 4.48 (s, 2H), 1.52 (s, 6H).

    Example 15

    Preparation of C817

    [0202] ##STR00046##

    [0203] In an argon filled glovebox, 1,3-bis(2,4,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-ium bromide (0.300 g, 0.683 mmol), sodium tert-butoxide (0.0656 g, 0.683 mmol), and C823 (0.281 g, 0.342 mmol) were weighed into separate 40 mL scintillation vials equipped with magnetic stir bars and each dissolved/suspended in tetrahydrofuran (10 mL). The solutions/suspensions were cooled to 35 C. then the solution of sodium tert-butoxide was added to the solution of 1,3-bis(2,4,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-ium bromide over 2 minutes. The reaction was stirred at 35 C. for 30 minutes then combined with the chilled suspension of C823 and stirred for an additional 30 minutes at 35 C. before allowing the reaction to slowly warm to ambient temperature overnight. The reaction was subsequently devolatilized, triturated with hexanes (240 mL), dissolved in toluene (10 mL), and filtered through celite. The crude solution was combined with a solution of 1-isopropoxy-2-(prop-1-en-1-yl)benzene (0.301 g, 1.71 mmol) in toluene (2 mL) and stirred overnight at ambient temperature. The resulting solution was diluted with hexanes (15 mL) to afford a green precipitate which was isolated by filtration and washed with toluene/hexanes (1:10, 210 mL). The precipitate was dissolved in tetrahydrofuran (5 mL) and combined with (3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.086 g, 0.26 mmol) in a 20 mL scintillation vial equipped with a magnetic stir bar. The resulting reaction was stirred at ambient temperature for 60 minutes then devolatilized, dissolved in dichloromethane, filtered, and recrystallized from dichloromethane/diethyl ether at 35 C. The resulting yellow/brown crystals were washed with cold diethyl ether (23 mL) then dried under vacuum to afford C817 (0.0462 g, 16.5% yield overall).

    [0204] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) [two conformers in solution, 40:60] 14.54 br s (0.4H), 14.44 (br s, 0.6H), 7.43-7.34 (m, 1H), 7.11 (d, J=8.6 Hz, 1H), 6.97-6.89 (m, 2H), 6.88-6.81 (m, 2H), 6.77-6.67 (m, 1H), 6.40-6.64 (m, 2H), 5.95-5.82 (m, 1H), 5.52-5.35 (m, 1H), 3.90 (br s, 1.2H), 3.75 (br s, 0.8H), 1.88-1.74 (m, 6H), 1.45-1.29 (m, 6H).

    Stereoretentive Self-Metathesis of Internal Olefins

    Example 16

    Self-Metathesis of Cis or Trans-5-Tetradecene (5C14)

    [0205] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with C765 (4.5 mg, 0.0059 mmol) and tetrahydrofuran (1 mL). 5-Tetradecene (cis or trans) (0.150 mL, 0.588 mmol) was subsequently added, the vial sealed and heated to 40 C. for 2 hours. Yields and stereoselectivies were determined by gas chromatography (method 1).

    TABLE-US-00002 TABLE 1 [00047]embedded image 5C14 (cis:trans) % 5C14 (Z/E) % 5C10 (Z/E) % 9C18 cis > 98% 50 (97/3) 25 (97/3) 25 trans > 98% 54 (4/96) 23 (5/95) 23

    [0206] Unexpectedly, after 2 hours at 40 C., reactions of either cis or trans-5C14 (>98% stereoisomerically pure) catalyzed by 1 mol % C765 reached a near equilibrium distribution of products while retaining the stereochemistry of the starting material in high fidelity.

    Example 17

    Self-Metathesis of Various Ratios of Cis and Trans-5-Tetradecene (5C14)

    [0207] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with C765 (4.5 mg, 0.0059 mmol) and tetrahydrofuran (1 mL). 5-Tetradecene (cis/trans) (0.150 mL total, 0.588 mmol) in an appropriate ratio was subsequently added, the vial sealed and stirred at ambient temperature. Reactions were sampled at 2 and 4 hour time points and yields/stereoselectivies were determined by gas chromatography (method 1).

    TABLE-US-00003 TABLE 2 [00048]embedded image % entry 5C14 (cis:trans) time (h) % 5C14 (Z/E) % 5C10 (Z/E) 9C18 1 cis >98% 2 54 (95/5) 23 (95/5) 23 4 52 (94/6) 24 (94/6) 24 2 90:10 2 54 (74/26) 23 (90/10) 23 4 53 (72/28) 23 (87/13) 24 3 50:50 2 64 (36/64) 18 (73/27) 18 4 63 (36/64) 19 (68/32) 18 4 10:90 2 86 (9/91) 7 (49/51) 7 4 84 (8/92) 8 (47/53) 8 5 trans >98% 2 82 (2/98) 9 (11/89) 9 4 80 (2/98) 10 (10/90) 10

    [0208] Table 2 summarizes a series of reactions where C765 (0.5 mol %) was exposed to various ratios of cis and trans-5C14. While good stereoretention is attainable when isomerically pure starting material is used (entries 1 and 5), product distributions from reactions with mixtures of cis and trans-5C14 were complicated by the difference in reactivity of cis and trans stereoisomers.

    Example 18

    Self-Metathesis of Cis-5-Tetradecene (5C14)

    [0209] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with C849z (10-5000 ppm) and tetrahydrofuran (1 mL). cis-5-Tetradecene (0.150 mL, 0.588 mmol) was subsequently added, the vials sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 1).

    TABLE-US-00004 TABLE 3 [00049]embedded image entry C849z (ppm) time (min) % 5C14 (Z/E) % 5C10 (Z/E) % 9C18 % isomers 1 5000 30 47 (92/8) 23 (91/9) 24 6 60 42 (90/10) 21 (88/12) 22 15 120 36 (81/19) 18 (81/19) 18 28 2 1000 30 50 (95/5) 25 (95/5) 24 1 60 49 (94/6) 25 (94/6) 24 2 3 500 30 49 (95/5) 25 (96/4) 25 1 60 50 (95/5) 25 (95/5) 24 1 4 100 30 52 (96/4) 24 (96/4) 24 <1 60 52 (96/4) 24 (96/4) 24 <1 5 50 30 51 (95/5) 25 (96/4) 24 <1 60 51 (94/6) 25 (96/4) 24 <1

    [0210] We increased the steric bulk of the NHC ligand and prepared C849z. Reactions of C849z with cis-5C14 were initially hindered by high catalyst activity (entry 1), as a loading of 5000 ppm (0.5 mol %) afforded a significant amount of isomers and eroded the stereoselectivity of the transformation rapidly. Reducing the catalytic charge (1000 to 50 ppm; entries 2-5) afforded equilibrium distributions within 1 hour with good stereoretention.

    Example 19

    Self-Metathesis of Various Ratios of Cis and Trans-5-Tetradecene (5C14)

    [0211] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with C849z (500 ppm) and tetrahydrofuran (1 mL). 5-Tetradecene (cis/trans) (0.150 mL total, 0.588 mmol) in an appropriate ratio was subsequently added, the vial sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 1).

    TABLE-US-00005 TABLE 4 [00050]embedded image 5C14 entry (cis:trans) time (min) % 5C14 (Z/E) % 5C10 (Z/E) % 9C18 1 cis >98% 30 63 (95/5) 19 (95/5) 18 60 56 (94/6) 22 (95/5) 22 120 54 (93/7) 23 (95/5) 23 240 54 (93/7) 24 (95/5) 23 2 90:10 30 60 (77/23) 20 (96/4) 20 60 57 (76/24) 21 (96/4) 21 120 57 (75/25) 22 (96/4) 21 240 57 (75/25) 22 (96/4) 21 3 50:50 30 74 (33/67) 13 (92/8) 13 60 73 (33/67) 14 (90/10) 13 120 73 (33/67) 14 (88/12) 14 240 73 (33/67) 14 (88/12) 14 4 10:90 30 91 (7/93) 4 (80/20) 4 60 91 (8/92) 5 (74/26) 5 120 91 (8/92) 5 (72/28) 5 240 91 (8/92) 5 (72/28) 5 5 trans >98% 30 98 (2/98) 1 (64/36) <1 60 97 (2/98) 1 (61/39) 1 120 97 (2/98) 1 (59/41) 1 240 97 (2/98) 1 (58/42) 1

    [0212] Using an optimized catalyst loading, Table 4 summarizes a series of reactions where C849z (500 ppm) was exposed to various ratios of cis and trans-5C14. Unlike C765, C849z afforded product distributions that approach theoretical, when the trans-5-tetradecene is considered an unreactive stereoisomer.

    Example 20

    Self-Metathesis of Cis or Trans-Methyl-9-Octadecenoate (MO)

    [0213] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with either C765 (0.5-7.5 mol %) or C849z (100 ppm) and tetrahydrofuran (1 mL). Methyl-9-octadecenoate (cis or trans) (0.150 mL, 0.442 mmol) was subsequently added, the vial sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 2). DE is 1,18-dimethyl ester of 9-octadecene and 9C18 is 9-octadecene.

    TABLE-US-00006 TABLE 5 [00051]embedded image [00052]embedded image entry Ru (mol %) MO (cis:trans) time (h) % MO (Z/E) % DE (Z/E) % 9C18 (Z/E) 1 C849z (0.01) cis >99% 0.5 64 (>99/1) 18 (>99/1) 18 (>99/1) 1.5 53 (>99/1) 23 (>99/1) 24 (>99/1) 2 52 (>99/1) 24 (>99/1) 24 (>99/1) 2 C849z (0.01) trans >97% 0.5 100 (<1/99) ND.sup.a ND.sup.a 1.5 100 (<1/99) ND.sup.a ND.sup.a 2 100 (<1/99) ND.sup.a ND.sup.a 3 C765 (0.5) cis >99% 0.5 90 (>99/1) 5 (>99/1) 5 (>99/1) 1.5 84 (>99/1) 8 (>99/1) 8 (>99/1) 2 80 (>99/1) 10 (>99/1) 10 (>99/1) 4 C765 (0.5) trans >97% 2 100 (<1/99) ND.sup.a ND.sup.a 5 C765 (2.5) trans >97% 4 98 (<1/99) 1 (<1/99) 1 (<1/99) 20 92 (<1/99) 4 (<1/99) 4 (<1/99) 6 C765 (5.0) trans >97% 4 93 (<1/99) 3 (<1/99) 3 (<1/99) 20 72 (1/99) 14 (3/97) 14 (3/97) 7 C765 (7.5) trans >97% 4 80 (<1/99) 10 (<1/99) 10 (<1/99) 20 52 (4/96) 24 (4/96) 24 (4/96) .sup.anot detected

    [0214] The self-metathesis of methyl-9-octadecenoate (MO) was subsequently examined to determine the effect of modest functionality on the transformation (Table 5). Exposing cis-methyl-9-octadecenoate to C849z (0.1 mol %) afforded an equilibrium distribution of product within 2 hours with excellent stereoretention (>99% Z) (entry 1). At this same loading, no reaction was observed with trans-methyl-9-octadecenoate (entry 2). A higher catalyst loading of C765 (0.5 mol %) afforded 20% conversion of cis-methyl-9-octadecenoate while failing to afford any reaction with trans-methyl-9-octadecenoate after 2 hours (entries 3 and 4). Increasing the catalyst loading of C765 restored reactivity with trans-methyl-9-octadecenoate (entries 5-7) and after 20 hours, C765 (7.5 mol %) afforded a near equilibrium distribution of products with good stereoretention (96% E).

    Example 21

    Self-metathesis of various ratios of cis and trans-Methyl-9-octadecenoate (MO)

    [0215] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with C849z (1000 ppm) and tetrahydrofuran (1 mL). Methyl-9-octadecenoate (cis/trans) (0.150 mL total, 0.442 mmol) was subsequently added, the vial sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 2).

    TABLE-US-00007 TABLE 6 [00053]embedded image [00054]embedded image [00055]embedded image MO entry (cis:trans) time (min) % MO (Z/E) % DE % 9C18 (Z/E) 1 Cis >99% 30 50 (>99/1) 25 25 (>99/1) 60 50 (>99/1) 25 25 (>99/1) 120 50 (>99/1) 25 25 (>99/1) 240 50 (>99/1) 25 25 (98/2) 2 80:20 30 80 (75/25) 10 10 (>99/1) 60 72 (72/27) 14 14 (97/3) 120 68 (70/30) 16 16 (97/3) 240 66 (68/32) 17 17 (96/4) 3 50:50 30 91 (46/54) 5 5 (>99/1) 60 88 (44/56) 6 6 (>99/1) 120 86 (42/58) 7 7 (>99/1) 240 85 (42/58) 7 7 (>99/1) 4 20:80 30 100 (20/80) ND.sup.a ND.sup.a 60 99 (20/80) <1 <1 (>99/1) 120 99 (20/80) 1 1 (>99/1) 240 99 (20/80) 1 1 (>99/1) 5 trans >97% 30 100 (<1/99) ND.sup.a ND.sup.a 60 100 (<1/99) ND.sup.a ND.sup.a 120 100 (<1/99) ND.sup.a ND.sup.a 240 100 (<1/99) ND.sup.a ND.sup.a .sup.anot detected

    [0216] Table 6 summarizes a series of reactions where C849z (1000 ppm) was exposed to various ratios of cis and trans-methyl-9-octadecenoate. Reactions with 80 or 100% cis-methyl-9-octadecenoate (entries 1 and 2) afforded near theoretical product distributions after 4 hours with excellent stereoretention. Reactions conducted with an increased trans-methyl-9-octadecenoate content (entries 3-5) afforded very little reactivity although products maintained high fidelity.

    Example 22

    Self-Metathesis of Cis or Trans-2-Hexene

    [0217] In an argon filled glovebox, a 40 mL scintillation vial equipped with a magnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL). 2-Hexene (cis or trans) (0.100 mL, 0.815 mmol) was subsequently added, the vial sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 1).

    TABLE-US-00008 TABLE 7 [00056]embedded image [00057]embedded image entry Ru (mol %) cis/trans time (h) % conv % yield Z/E 1 C849z (0.05) cis 1 48 44 98/2 2 49 44 97/3 6 50 44 96/4 2 trans 1 NR.sup.a NR.sup.a ND.sup.b 2 NR.sup.a NR.sup.a ND.sup.b 6 NR.sup.a NR.sup.a ND.sup.b 3 C765 (0.5) cis 1 48 44 98/2 2 49 44 97/3 6 51 44 92/8 4 trans 1 <1 <1 ND.sup.b 2 2 2 36/64 6 4 4 25/75 5 C745 (0.5) cis 1 46 44 99/1 2 48 44 97/3 6 50 45 94/6 6 trans 1 1 1 <1/99 2 4 4 <1/99 6 23 23 <1/99 .sup.ano reaction observed .sup.bnot determined

    [0218] While C849z, in comparison with C765, afforded a greater disparity in the reactivity of cis and trans substrates, we sought to identify a catalyst with an improved rate of reactivity with trans substrates. Reducing the steric bulk of the ortho-substituents of the NHC ligand afforded C745. C849z, C765 and C745 were subsequently screened as catalysts for the self-metathesis of 2-hexene (Table 7). Reactions of cis-2-hexene (entries 1, 3, and 5) reached maximum conversion/yield within 1 hour with excellent stereoretention (>98% Z). Under the same conditions, trans-2-hexene afforded little to no conversion (4%) after 6 hours when exposed to C765 (0.5 mol %) or C849z (0.05 mol %) (entries 2 and 4). Gratifyingly, C745 (0.5 mol %) afforded 23% yield after 6 hours with excellent stereoretention (>99% E) (entry 6).

    Stereoretentive Cross Metathesis of Internal Olefins

    Example 23

    Cross Metathesis of 4-Octene (4C8) with 1,4-Diacetoxy-2-butene (1,4-DAB)

    [0219] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with catalyst and tetrahydrofuran (0.50 mL). 4-Octene (0.100 mL, 0.64 mmol) and 1,4-diacetoxy-2-butene (0.406 mL, 2.55 mmol) were subsequently added, the vial sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 2).

    TABLE-US-00009 TABLE 8 [00058]embedded image [00059]embedded image [00060]embedded image entry C765 (mol %) 4C8/1,4-DAB time (h) % conv % yield Z/E.sup.a 1 3.0 cis/cis 0.25 54 49 >99/1 1.5 94 91 >99/1 2.5 95 91 >99/1 5 95 91 >99/1 2 5.0 trans/trans 1 9 6 <1/99 2 15 11 <1/99 4 19 17 <1/99 5 22 20 <1/99 72 33 31 <1/99 3 7.5 trans/trans 1 15 11 <1/99 2 21 19 <1/99 4 30 27 <1/99 5 33 31 <1/99 72 50 47 <1/99 .sup.a2-hexenyl acetate (2C6 OAc)

    [0220] The cross metathesis of 4-octene and 1,4-diacetoxy-2-butene was examined (Table 8). Contacting a mixture of cis-1,4-diacetoxy-2-butene and cis-4-octene (4:1) with C765 (3.0 mol %) afforded cis-2-hexenyl acetate in 91% yield (>99% Z) (entry 1). Reactions between trans-1,4-diacetoxy-2-butene and trans-4-octene were considerably slower (entries 2 and 3) but after 3 days, a mixture of trans-1,4-diacetoxy-2-butene and trans-4-octene (4:1) with C765 (7.5 mol %) afforded trans-2-hexenyl acetate in 47% yield (>99% E).

    Example 24

    Cross Metathesis of trans-4-Octene with trans-1,4-Diacetoxy-2-butene

    [0221] In an argon filled glovebox, a 4 mL scintillation vial equipped with a magnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL). Trans-4-octene (0.050 mL, 0.32 mmol) and trans-1,4-diacetoxy-2-butene (0.203 mL, 1.27 mmol) were subsequently added, the vial was sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 2).

    TABLE-US-00010 TABLE 9 [00061]embedded image [00062]embedded image [00063]embedded image entry Ru time (h) % yield.sup.a Z/E.sup.a 1 C765 1 0 ND.sup.b 2 2 <1/99 4 4 <1/99 72 13 <1/99 2 C745 1 2 <1/99 2 5 <1/99 4 11 <1/99 72 24 <1/99 3 C781 1 4 <1/99 2 7 <1/99 4 14 <1/99 72 28 <1/99 4 C817 1 3 <1/99 2 6 <1/99 4 11 <1/99 72 27 <1/99 5 C905 1 2 <1/99 2 2 <1/99 4 4 <1/99 48 4 <1/99 .sup.a2C6 OAc .sup.bnot determined

    [0222] Focusing our efforts on identifying catalysts with improved reactivity toward trans substrates, C781, C817 and C905 were prepared. Contacting a mixture of trans-1,4-diacetoxy-2-butene and trans-4-octene (4:1) with ruthenium catalyst (3.0 mol %) afforded trans-2-hexenyl acetate (Table 9). After 3 days, C765 afforded 13% yield of trans-2-hexenyl acetate (entry 1) whereas C745, C781 and C817 afforded 24-28% yield (entries 2-4). C905 performed poorly affording <5% yield (entry 5).

    Stereoretentive Cross Metathesis of Terminal Olefins with Internal Olefins

    Example 25

    Cross Metathesis of Allyl Acetate with Cis or Trans-4-Octene

    [0223] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL). 4-Octene (cis or trans) (0.120 mL, 0.75 mmol) and allyl acetate (0.050 mL, 0.38 mmol) were subsequently added, the vial sealed and stirred at 30 C. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 2).

    TABLE-US-00011 TABLE 10 [00064]embedded image [00065]embedded image [00066]embedded image entry cis/trans Ru time (h) % conv % yield.sup.a Z/E.sup.a 1 cis C765 2 28 28 >99/1 4 28 28 >99/1 22 28 28 >99/1 2 trans C765 2 ND.sup.b ND.sup.b ND.sup.b 4 ND.sup.b ND.sup.b ND.sup.b 22 ND.sup.b ND.sup.b ND.sup.b 3 cis C849z 2 22 22 >99/1 4 22 22 >99/1 22 22 22 >99/1 4 trans C849z 2 ND.sup.b ND.sup.b ND.sup.b 4 ND.sup.b ND.sup.b ND.sup.b 22 ND.sup.b ND.sup.b ND.sup.b .sup.a2C6 OAc .sup.bnot detected

    [0224] A mixture of allyl acetate and cis or trans-4-octene was combined with C849z or C765 (3 mol %) (Table 10). After 22 hours, reactions of cis-4-octene and C849z or C765 afforded 22 and 28% yield of cis-2-hexenyl acetate (>99% Z), respectively (entries 1 and 3). No reactions were observed with trans-4-octene under these conditions (entries 2 and 4).

    Example 26

    Cross Metathesis of Allyl Benzene with Cis or Trans-4-Octene

    [0225] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL). 4-Octene (cis or trans) (0.120 mL, 0.75 mmol) and allyl benzene (0.059 mL, 0.38 mmol) were subsequently added, the vial sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 2).

    TABLE-US-00012 TABLE 11 [00067]embedded image [00068]embedded image [00069]embedded image entry Ru cis/trans time (h) % conv % yield.sup.a Z/E.sup.a 1 C849z cis 2 91 77 99/1 4 92 77 99/1 2 trans 2 31 2 <1/99 4 33 2 <1/99 3 C765 cis 2 55 45 93/7 4 61 46 88/12 4 trans 2 23 9 8/92 4 31 9 10/90 5 C745 cis 2 81 61 96/4 4 82 62 95/5 6 trans 2 60 32 3/97 4 64 32 3/97 .sup.a1-phenyl-2-hexene 1Ph2C6

    [0226] A mixture of allyl benzene and cis or trans-4-octene was combined with C849z, C765 or C745 (3 mol %) (Table 11). After 4 hours, reactions with cis-4-octene and C849z, C765 or C745 afforded 77, 46, and 62% yield respectively (entries 1, 3, and 5) with good stereoretention. Conversions were 10-20% higher than the observed yields with the major byproduct resulting from secondary self-metathesis of 1-phenyl-2-hexene to afford 1,4-diphenyl-2-butene. Reactions were conducted in the same fashion with trans-4-octene and C849z, C765 or C745 afforded 2, 9, and 32% yield respectively (entries 2, 4, and 6) with good to excellent stereoretention. Conversions were 20-30% higher than the observed yields with the major byproduct resulting from isomerization of allyl benzene to -methylstyrene.

    Example 27

    Cross Metathesis of 1-Decene (1C10) with is or trans-4-Octene

    [0227] In an argon filled glovebox, a 20 mL scintillation vial equipped with a magnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL). 4-Octene (cis or trans) (0.083 mL, 0.53 mmol) and 1-decene (0.050 mL, 0.26 mmol) were subsequently added, the vial sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 1).

    TABLE-US-00013 TABLE 12 [00070]embedded image [00071]embedded image [00072]embedded image entry Ru cis/trans time (h) % conv % yield.sup.a Z/E.sup.a 1 C849z cis 2 90 75 97/3 5 89 74 96/4 2 trans 2 91 4 12/88 5 92 4 13/88 3 C765 cis 2 79 64 96/4 5 87 64 90/10 4 trans 2 28 11 9/91 5 48 13 13/87 5 C745 cis 2 86 71 93/7 5 88 73 92/8 6 trans 2 63 46 6/94 5 67 47 7/93 .sup.a4C13

    [0228] A mixture of 1-decene and cis or trans-4-octene was combined with C849z, C765 or C745 (3.0 mol %) in tetrahydrofuran (1.0 mL) (Table 12). After 5 hours, reactions with cis-4-octene and C849z, C765 or C745 afforded 74, 64, and 73% yield of cis-4-tridecene (4C13), respectively, with good stereoretention (entries 1, 3, and 5). Conversions were 15-23% higher than the observed yields with the major byproduct (9-octadecene) resulting from secondary self-metathesis. Exchanging cis-4-octene with trans-4-octene afforded less productive reactions as C849z, C765 or C745 afforded 4, 13, and 47% yield of trans-4-tridecene, respectively, with good stereoretention (entries 2, 4, and 6). Conversions for all transformations were significantly higher than the yields observed (20-88%) and can be attributed to undesired isomerization of 1-decene to 2-decene and 4-octene to 3-octene. The isomerized products also form cis-trans isomers which are proposed to attribute to the 4% product in entry 2. 9-Octadecene is observed which results for the product 4-tetradecene undergoing additional metathesis to yield 9-octadecene and 4-octene.

    Example 28

    Cross Metathesis of 1-Decene with cis or trans-4-Octene

    [0229] In an argon filled glovebox, a 4 mL scintillation vial equipped with a magnetic stir bar was charged with catalyst and tetrahydrofuran (2 mL). 4-Octene (cis or trans) (0.125 mL, 0.79 mmol) and 1-decene (0.050 mL, 0.26 mmol) were subsequently added, the vial sealed and stirred at ambient temperature. Reactions were sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (method 1).

    TABLE-US-00014 TABLE 13 [00073]embedded image [00074]embedded image [00075]embedded image entry Ru cis/trans time (h) % conv % yield.sup.a Z/E.sup.a 1 C765 cis 1 84 55 >99/1 2 85 55 >99/1 4 84 58 >99/1 2 trans 1 36 7 <1/99 2 36 7 <1/99 4 36 7 <1/99 3 C745 cis 1 82 58 >99/1 2 87 59 97/3 4 88 57 97/3 4 trans 1 50 21 <1/99 2 54 26 <1/99 4 53 29 <1/99 5 C781 cis 1 66 42 >99/1 2 74 49 >99/1 4 79 54 >99/1 6 trans 1 43 19 <1/99 2 51 25 <1/99 4 53 31 <1/99 7 C817 cis 1 56 48 98/2 2 58 57 98/2 4 76 65 97/3 8 trans 1 32 25 1/99 2 42 32 2/98 4 50 39 2/98 9 C905 cis 1 21 21 87/13 2 25 24 87/13 4 25 24 87/13 10 trans 1 ND.sup.b ND.sup.b ND.sup.b 2 ND.sup.b ND.sup.b ND.sup.b 4 ND.sup.b ND.sup.b ND.sup.b .sup.a4-tridecene 4C13 .sup.bnot detected

    [0230] A mixture of 1-decene and cis-4-octene was combined with C765, C745, C781, C817, or C905 (3.0 mol %) in tetrahydrofuran (2.0 mL) (Table 13). After 4 hours, C765, C745, C781 and C817 afforded 54-65% yield of cis-4-tridecene with excellent stereoretention (>97% Z) (entries 1, 3, 5, and 7). Exchanging cis-4-octene with trans-4-octene afforded less productive reactions as C765, C745, C781 and C817 afforded 7-39% yield of trans-4-tridecene with excellent stereoretention (>98% E) (entries 2, 3, 6, and 8). C905 performed poorly affording only 24% for the cross metathesis of 1-decene and cis-4-octene and no reaction was observed with trans-4-octene.

    Example 29

    [0231]

    TABLE-US-00015 Self-metathesis reaction [00076]embedded image [00077]embedded image Substrate Time (hr) % E 5 % E 6 % E 4 4a.sup.a 0.5 >97 >97 >98 1 >98 >96 99 2 >97 >98 98 5 >99 >98 >99 4b.sup.a 0.5 100.0 100.0 100.0 1 >98 100.0 100.0 2 >99 >99 98 5 99 >97 98 .sup.aQuantitative data determined by gas chromatography.

    Example 30

    [0232]

    TABLE-US-00016 Self-metathesis reaction [00078]embedded image [00079]embedded image Percent Substrate Time (hr) % E 5 % E 6 % E 4 Conversion 4c.sup.a 1 >98 >98 >98 3.9 7 >98 >98 >98 9.5 12 >98 >98 >98 12.4 18 >98 >98 >98 13.3 23 >98 >98 >98 14.2 4d.sup.a 1 >98 >98 >98 2.1 7 >98 >98 >98 6.8 12 >98 >98 >98 9.6 18 >98 >98 >98 12.0 22 >98 >98 >98 13.2 .sup.aQuantitative data determined by .sup.1H NMR. Reactions were ran in a J. Young tube in THF-d.sub.8.

    Example 31

    [0233]

    TABLE-US-00017 Cross metathesis reaction [00080]embedded image [00081]embedded image [00082]embedded image Percent Time (hr) % E 7.sup.a % E 8.sup.a % E 9.sup.a Conversion.sup.a 1 >98 >98 >98 0.8 7 >98 >98 >98 4.2 12 >98 >98 >98 6.4 18 >98 >98 >98 8.2 24 >98 >98 >98 9.9 48 >98 >98 >98 12.5 .sup.aQuantitative data determined by .sup.1H NMR. Reactions were ran in a J. Young tube in THF-d.sub.8.