NOVEL RUTHENIUM COMPLEXES, METHOD OF THEIR SYNTHESIS, INTERMEDIATE COMPOUNDS USED IN THIS METHOD, METHOD OF THEIR SYNTHESIS AND USE OF NOVEL RUTHENIUM COMPLEXES IN OLEFIN METATHESIS REACTIONS

Abstract

The object of the invention is a novel ruthenium complex of the general formula Ru-1, in which all the variable substituents have the meanings defined in the description. Also an object of the invention is a method for obtaining the ruthenium complex, a ligand precursor intermediate compound used in the preparation of the ruthenium complex CAAC-1 and the use of this ruthenium complex as a (pre)catalyst in olefin metathesis reactions.

Claims

1. A precursor of cyclic alkylamine carbenes (CAAC) of the formula CAAC-1 ##STR00109## wherein X denotes an anion selected from the group comprising halogen atom, BF.sub.4.sup., PF.sub.6.sup., ClO.sub.4.sup., CF.sub.3SO.sub.2O.sup.; R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently denote a hydrogen atom, a C.sub.1-C.sub.12 alkyl group, a C.sub.3-C.sub.12 cycloalkyl group, a C.sub.5-C.sub.20 aryl group or a C.sub.5-C.sub.20 heteroaryl group, a C.sub.5-C.sub.25 aralkyl group, which may be substituted independently by one and/or more substituents selected from the group comprising a hydrogen atom, a halogen atom, a C.sub.1-C.sub.12 alkyl group, a C.sub.1-C.sub.12 perfluoroalkyl group, a C.sub.5-C.sub.20 aryl group, a C.sub.5-C.sub.20 perfluoroaryl group, a C.sub.5-C.sub.20 heteroaryl group, a C.sub.1-C.sub.12 alkoxyl group, a C.sub.5-C.sub.24 aryloxyl group, a C.sub.5-C.sub.20 heteroaryloxyl group, a sulfide (SR) group, an amino (NR.sub.2) group, in which the R group independently denotes a hydrogen atom, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, alternatively R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are connected to form a C.sub.5-C.sub.25 ring; each substituent R.sup.6, R.sup.7, and R.sup.8 denotes a hydrogen atom, a halogen atom, a C.sub.1-C.sub.12 alkyl group, or a C.sub.5-C.sub.20 aryl group, which may be substituted independently by one and/or more substituents selected from the hydrogen-containing group, a C.sub.1-C.sub.12 alkyl group, a C.sub.1-C.sub.12 perfluoroalkyl group, a C.sub.5-C.sub.20 aryl group, a C.sub.5-C.sub.20 perfluoroaryl group, a C.sub.5-C.sub.20 heteroaryl group, a C.sub.1-C.sub.12 alkoxyl group, a C.sub.5-C.sub.24 aryloxyl group, a C.sub.5-C.sub.20 heteroaryloxyl or a halogen atom, a sulfide group (SR), an amino group (NR.sub.2), in which the R group independently denotes a hydrogen atom, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl; R.sup.9 substituent means a substituted or unsubstituted heterocyclic group or an organometallic complex group selected from thiophene, benzothiophene, furan, benzofuran or ferrocene, which can be substituted independently by one and/or more substituents selected from the group comprising a hydrogen atom, a halogen atom, a C.sub.1-C.sub.12 alkyl group, a C.sub.1-C.sub.12 perfluoroalkyl group, a C.sub.5-C.sub.20 aryl group, a C.sub.5-C.sub.20 perfluoroaryl group, a C.sub.5-C.sub.20 heteroaryl group, a C.sub.1-C.sub.12 alkoxyl group, a C.sub.5-C.sub.24 aryloxyl group, a C.sub.5-C.sub.20 heteroaryloxyl group, a sulfide group (SR), an amino group (NR.sub.2), wherein the R group independently denotes a hydrogen atom, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl.

2-3. (canceled)

4. The precursor of the formula CAAC-1 according to claim 1, having the structure represented by the formula L1, L2, L3, L4, L5, L6, L7, L8, L9, L10, L11, L12, L13, L14, L15, L16, L17, L18, L19, L20, L21 or L22: ##STR00110## ##STR00111##

5. A ruthenium complex of formula 1-Ru ##STR00112## wherein: X.sup.1 and X.sup.2 independently of each other denote an anionic ligand selected from the group comprising a halogen anion, a CN, SCN, OR.sup.a, SR.sup.a, O(CO)R.sup.a, O(SO.sub.2)R.sup.a and OSi(R.sup.a).sub.3 group, wherein R.sup.a denotes C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl or C.sub.5-C.sub.20 aryl, which is optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxyl, C.sub.5-C.sub.24 aryloxyl, C.sub.5-C.sub.20 heteroaryloxyl or a halogen atom; R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 denote independently a hydrogen atom, a C.sub.1-C.sub.12 alkyl group, a C.sub.3-C.sub.12 cycloalkyl group, a C.sub.5-C.sub.20 aryl group or a C.sub.5-C.sub.20 heteroaryl group, a C.sub.5-C.sub.25 aralkyl group, which may be independently substituted with one and/or more substituents selected from the group comprising a hydrogen atom, a halogen atom, a C.sub.1-C.sub.12 alkyl group, a C.sub.1-C.sub.12 perfluoroalkyl group, a C.sub.5-C.sub.20 aryl group, a C.sub.5-C.sub.20 perfluoroaryl group, a C.sub.5-C.sub.20 heteroaryl group, a C.sub.1-C.sub.12 alkoxyl group, a C.sub.5-C.sub.24 aryloxyl group, a C.sub.5-C.sub.20 heteroaryloxyl group, a sulfide group (SR), an amino group (NR.sub.2), in which the R group independently denotes a hydrogen atom, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, alternatively R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are bonded with each other to form a C.sub.5-C.sub.25 ring; each substituent R.sup.6, R.sup.7, and R.sup.8 denotes a hydrogen atom, a halogen atom, a C.sub.1-C.sub.12 alkyl group, or a C.sub.5-C.sub.20 aryl group, which may be substituted independently with one and/or more substitutes selected from the group comprising a hydrogen atom, a C.sub.1-C.sub.12 alkyl group, a C.sub.1-C.sub.12 perfluoroalkyl group, a C.sub.5-C.sub.20 aryl group, a C.sub.5-C.sub.20 perfluoroaryl group, a C.sub.5-C.sub.20 heteroaryl group, C.sub.1-C.sub.12 alkoxyl group, a C.sub.5-C.sub.24 aryloxyl group, a C.sub.5-C.sub.20 heteroaryloxyl group or halogen atom, a sulfide group (SR), an amino group (NR.sub.2), in which the group R independently denotes a hydrogen atom, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl; R.sup.9 substituent denotes a substituted or unsubstituted heterocyclic group and/or organometallic complex group selected from thiophene, benzothiophene, furan, benzofuran or ferrocene, which may be substituted independently with one and/or more substituents selected from the group comprising a hydrogen atom, a halogen atom, a C.sub.1-C.sub.12 alkyl group, a C.sub.1-C.sub.12 perfluoroalkyl group, a C.sub.5-C.sub.20 aryl group, a C.sub.5-C.sub.20 perfluoroaryl group, a C.sub.5-C.sub.20 heteroaryl group, a C.sub.1-C.sub.12 alkoxyl group, a C.sub.5-C.sub.24 aryloxyl group, a C.sub.5-C.sub.20 heteroaryloxyl group, a sulfide group (SR), an amino group (NR.sub.2), in which the R group denotes independently a hydrogen atom, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, R.sup.16 and R.sup.17 denote independently a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 aryloxyl, C.sub.6-C.sub.25 arylalkyl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 heteroaryloxyl, C.sub.5-C.sub.25 perfluoroaryl, a 3-12-membered heterocycle comprising a sulfur, oxygen, nitrogen, selenium or a phosphorus atom; whereby the substituents R.sup.16 and R.sup.17 may be linked together to form a ring selected from the group comprising C.sub.3-C.sub.25 cycloalkyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 perfluoroaryl, a 3-12-membered heterocycle comprising a sulfur, oxygen, nitrogen, selenium or a phosphorus atom, which may be substituted independently by one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.7-C.sub.12 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 aryloxyl, C.sub.6-C.sub.25 arylalkyl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 heteroaryloxyl, C.sub.5-C.sub.25 perfluoroaryl, a 3-12-membered heterocycle; G is selected from such as ligand with the formula CAAC-1 ##STR00113## in which X and the substituents R.sup.1 to R.sup.9 have the above defined meanings either heteroatom 1 selected from the group comprising an oxygen atom, a sulfur atom, a selenium atom, substituted by a group selected from such as a hydrogen atom, a fluorine atom, an oxygen atom, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxyl, a 3-12-membered heterocycle, optionally substituted with an acyl group (COR), a cyano group (CN), a carboxyl group (COOH), an ester group (COOR), an ester group (CH.sub.2COOR), an ester group (CHRCOOR), an ester group (C(R).sub.2COOR), an amide group (CONR.sub.2), a Weinreb-type amide (CON(R)(OR)), a sulfone group (SO.sub.2R), a formyl group (CHO), a sulfonamide group (SO.sub.2NR.sub.2), a ketone group (COR), a thioamide group (CSNR.sub.2), a thioketone (CSR), a thionoester group (CSOR), a thioester group (COSR), a dithioester group (CS.sub.2R), in which the group R denotes independently C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, C.sub.5-C.sub.24 heteroaryloxyl and then the dashed line denotes a direct bond between a heteroatom and the substituent R.sup.17 or denotes a bond between the substituent R.sup.17 and a heteroatom via a methylene bridge CH.sub.2, CHR, or CR.sub.2 wherein the substituent R.sup.14 is C.sub.5-C.sub.15 aryl, optionally substituted with 1-4 substituents, independently selected from a group comprising a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxyl, a 3-12-membered heterocycle, an alkoxyl group (OR), a sulfide group (SR), a sulfoxide group (S(O)R), a sulfonium group (S.sup.+R.sub.2), a sulfone group (SO.sub.2R), a sulfonamide group (SO.sub.2NR.sub.2), an amino group (NR.sub.2), an ammonium group (N.sup.+R.sub.3), a nitro group (NO.sub.2), a cyano group (CN), a phosphinous group (P(O)(OR).sub.2), a phosphinic group (P(O)R(OR)), a phosphonine group (P(OR).sub.2), a phosphine group (PR.sub.2), a phosphine oxide group (P(O)R.sub.2), a phosphonium group (P.sup.+R3), a carboxyl group (COOH), an ester group (COOR), an amide group (CONR.sub.2), an amide group (NRC(O)R), a formyl group (CHO), a ketone group (COR), a thioamide group (CSNR.sub.2), a thioketone group (CSR), a thionoester group (CSOR), a thioester group (COSR), a dithioester group (CS.sub.2R), in which the R group denotes C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, or heteroatom 2 selected from a group comprising a nitrogen atom or a phosphorus atom, substituted with the group selected from such as a hydrogen atom, methylidene, optionally substituted with the substituent R, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxyl, a 3-12-membered heterocycle, an acyl group (COR), an ester group (COOR), a tert-butyl butyloxycarbonyl group (t-Boc) or a 9-fluorenylmethoxycarbonyla group (Fmoc), a carbamine group (CONR.sub.2), a sulfone group (SO.sub.2R), a formyl group (CHO), in which the R group denotes C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxyl, optionally substituted with an acyl group (COR), a cyano group (CN), a carboxyl group (COOH), an ester group (COOR), an ester group (CH.sub.2COOR), an ester group (CHRCOOR), an ester group (C(R).sub.2COOR), an amide group (CONR.sub.2), a sulfone group (SO.sub.2R), a formyl group (CHO), a sulfonamide group (SO.sub.2NR.sub.2), a ketone group (COR), a thioamide group (CSNR.sub.2), a thioketone group (CSR), a thionoester group (CSOR), a thioester group (COSR), a dithioester group (CS.sub.2R), in which the R group denotes C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxyl, and then the dashed line denotes a direct bond between the heteroatom and the substituent R.sup.14 or it denotes a bond between the substituent R.sup.17 with a heteroatom via methylene bridge (CH.sub.2), (CHR), or (CR.sub.2); wherein the substituent R.sup.17 is C.sub.5-C.sub.15 aryl, optionally substituted with 1-4 substituents independently selected from the group comprising a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxyl, a 3-12-membered heterocycle, an alkoxyl group (OR), a sulfide group (SR), a sulfoxide group (S(O)R), a sulfonium group (S.sup.+R.sub.2), a sulfone group (SO.sub.2R), a sulfonamide group (SO.sub.2NR.sub.2), an amino group (NR.sub.2), an ammonium group (N.sup.+R.sub.3), a nitro group (NO.sub.2), a cyano group (CN), a phosphinous group (P(O)(OR).sub.2), a phosphinic group (P(O)R(OR)), a phosphonine group (P(OR).sub.2), a phosphine group (PR.sub.2), a phosphine oxide group (P(O)R.sub.2), a phosphonium group (P.sup.+R.sub.3), a carboxyl group (COOH), an ester group (COOR), an amide group (CONR.sub.2), an amide group (NRC(O)R), a formyl group (CHO), a ketone group (COR), a thioamide group (CSNR.sub.2), a thioketone group (CSR), a thionoester group (CSOR), a thioester group (COSR), a dithioester group (CS.sub.2R), in which the group R denotes C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, or heteroatom 3 selected from a group comprising a halogen atom and then the dashed line denotes a direct bond between the heteroatom and the R.sup.17 substituent, wherein the R.sup.17 substituent is C.sub.5-C.sub.15 aryl, or C.sub.5-C.sub.25 polyaryl, optionally substituted with 1-4 substituents selected independently from a group comprising a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxyl, a 3-12-membered heterocycle, an alkoxy group (OR), a sulfide group (SR), a sulfoxide group (S(O)R), a sulfonium group (S.sup.+R.sub.2), a sulfone group (SO.sub.2R), a sulfonamide group (SO.sub.2NR.sub.2), an amino group (NR.sub.2), an ammonium group (N.sup.+R.sub.3), a nitro group (NO.sub.2), a cyano group (CN), a phosphonous group (P(O)(OR).sub.2), a phosphinous group (P(O)R(OR)), a phosphonine group (P(OR).sub.2), a phosphine group (PR.sub.2), a phosphine oxide group (P(O)R.sub.2), a phosphonium group (P.sup.+R.sub.3), a carboxyl group (COOH), an ester group (COOR), an amide group (CONR.sub.2), an amide group (NRC(O)R), a formyl group (CHO), a ketone group (COR), a thioamide group (CSNR.sub.2), a thioketone group (CSR), a thionoester group (CSOR), a thioester group (COSR), a dithioester group (CS.sub.2R), in which the R group denotes C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl.

6. The ruthenium complex according to claim 5 represented by the formula 1a-Ru ##STR00114## in which X.sup.1 and X.sup.2 and the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 substituents have the meanings defined above n means 1 or 0 Z is selected from a group comprising halogen atoms, O atom, S atom, Se atom, or a NR group, in which R denotes methylidene, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxyl, a 3-12-membered heterocycle, an acyl group (COR), an ester group (COOR), a tert-butyloxycarbonyl group (t-Boc) or a 9-fluorenylmethoxycarbonyl group (Fmoc), a carbamine group (CONR.sub.2), a sulfone group (SO.sub.2R), a formyl group (CHO), in which the R group denotes C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxyl, or a halogen atom, wherein if Z denotes a halogen atom, R.sup.18 is absent; R.sup.18 means independently a hydrogen atom, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.24 aryloxyl, a COOR group, a CH.sub.2COOR group, a CONR.sub.2 group, a CH.sub.2CONR.sub.2 group, a COR group, a CH.sub.2COR group, a CON(OR)(R) group, a CH.sub.2CON(OR)(R) group or a halogen atom, wherein R denotes C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 aryl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxyl, C.sub.6-C.sub.24 aryloxyl, or a halogen atom; R.sup.19, R.sup.20, R.sup.21, and R.sup.22 denote independently a hydrogen atom, a halogen atom, a C.sub.1-C.sub.25 alkyl group, a C.sub.2-C.sub.25 alkenyl group, a C.sub.5-C.sub.25 aryl group, an alkoxy group (OR), a sulfide group (SR), a sulfoxide group (S(O)R), a sulfonium group (S.sup.+R.sub.2), a sulfone group (SO.sub.2R), a sulfonamide group (SO.sub.2NR.sub.2), an amino group (NR.sub.2), an ammonium group (N.sup.+R.sub.3), a nitro group (NO.sub.2), a cyano group (CN), a phosphinous group (P(O)(OR).sub.2), a phosphinic group (P(O)R(OR)), a phosphonine group (P(OR).sub.2), a phosphine group (PR.sub.2), a phosphine oxide group (P(O)R.sub.2), a phosphonium group (P.sup.+R.sub.3), a carboxyl group (COOH), an ester group (COOR), an amide group (CONR.sub.2), an amide group (NRC(O)R), a formyl group (CHO), a ketone group (COR), a thioamide group (CSNR.sub.2), a thioketone group (CSR), a thionoester group (CSOR), a thioester group (COSR), a dithioester group (CS.sub.2R), in which the R group denotes C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, wherein the R.sup.16, R.sup.17, R.sup.18 and R.sup.19 substituents may be connected, thus forming a substituted or unsubstituted C.sub.4-C.sub.10 cyclic or C.sub.4-C.sub.12 polycyclic system.

7. The ruthenium complex according to claim 5 of the formula 1b-Ru ##STR00115## wherein X.sup.1 and X.sup.2 and the substituents R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 have the above defined meanings R.sup.16 and R.sup.17 denote independently a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, optionally substituted; C.sub.3-C.sub.25 cycloalkyl, optionally substituted; C.sub.1-C.sub.12 perfluoroalkyl, optionally substituted; C.sub.2-C.sub.25 alkene, optionally substituted; C.sub.2-C.sub.25 alkenyl, optionally substituted; C.sub.3-C.sub.25 cycloalkenyl, optionally substituted; C.sub.2-C.sub.25 alkynyl, optionally substituted; C.sub.3-C.sub.25 cycloalkyl, optionally substituted; C.sub.1-C.sub.25 alkoxyl, optionally substituted; C.sub.5-C.sub.25 aryl, optionally substituted; C.sub.5-C.sub.25 aryloxyl, optionally substituted; C.sub.6-C.sub.25 arylalkyl, optionally substituted; C.sub.5-C.sub.25 heteroaryl, optionally substituted; C.sub.5-C.sub.25 heteroaryloxyl, optionally substituted; C.sub.5-C.sub.25 perfluoroaryl, optionally substituted; a 3-12-membered heterocycle comprising a sulfur, oxygen, nitrogen, selenium or a phosphorus atom, optionally substituted; wherein the R.sup.16 and R.sup.17 substituents may be connected, forming a ring selected from a group comprising C.sub.3-C.sub.25 cycloalkyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 perfluoroaryl, a 3-12-membered heterocycle containing a sulfur, oxygen, nitrogen, selenium or phosphorus atom, which may be independently substituted with one or more substituents selected from a group comprising a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 aryloxyl, C.sub.6-C.sub.25 arylalkyl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 heteroaryloxyl, C.sub.5-C.sub.25 perfluoroaryl, a 3-12-membered heterocycle.

8. The ruthenium complex according to claim 5, which is selected from the complexes represented by the formulae of Ru1a, Ru2a, Ru3a, Ru4a, Ru5a, Ru6a, Ru7a, Ru8a, Ru9a, Ru10a, Ru11a, Ru11a, Ru12a, Ru13a, Ru14a, Ru15a, Ru16a, Ru17a, Ru18a, Ru19a, Ru20a, Ru21a, Ru22a: ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121##

9. Method for the synthesis of the ruthenium complex of the formula 1a-Ru ##STR00122## as defined in claim 6, characterized in that the alkylidene ruthenium complex of the formula 10 ##STR00123## wherein: L.sup.1 denotes a neutral ligand selected from the group comprising pyridine or substituted pyridine, P(R).sub.3, P(OR).sub.3, O(R).sub.2, N(R).sub.3, wherein each R independently denotes C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, a 5-12-membered heteroaryl; N, Z, X.sup.1, X.sup.2 and the substituents R.sup.18, R.sup.19, R.sup.20, R.sup.21 and R.sup.22 have the above defined meanings undergoes a reaction with the carbene of formula 8 ##STR00124## wherein the substituents R.sup.1 to R.sup.9 have the above defined meanings.

10. Use of the compound of formula 1-Ru, as defined in claim 5, as a precatalyst and/or catalyst in olefin metathesis reactions, particularly in ring-closing metathesis (RCM), cross-metathesis (CM), homometathesis (cross-metathesis between two molecules of the same olefin), ethenolysis, isomerization, in a diastereoselective ring rearrangement metathesis (DRRM) reaction, alkene-alkyne (ene-yn) metathesis or ROMP or ADMET polymerization reaction.

11. Use according to claim 10, wherein the reaction is carried out in an organic solvent such as toluene, mesitylene, hexane, cyclohexane, ethyl acetate, methyl acetate, methyl carbonate, ethyl carbonate, tertbutyl methyl ether, cyclopentyl methyl ether, diethyl ether, THF, 2 Me-THF, 4-Me-THP, dioxane, DME, PAO. PEG, paraffin, esters of saturated fatty acids.

12. Use according to claim 10, wherein the reaction is carried out in a solvent-free system.

13. Use according to claim 10, wherein the reaction is carried out at a temperature between 20 C. and 200 C.

14. Use according to claim 10, wherein the reaction is carried out over a period between 5 minutes and 48 hours.

15. Use according to claim 10, wherein the compound 1-Ru is applied in amount not exceeding 10 mol %.

16. Use according to claim 10, wherein the compound 1-Ru is applied in amount of not exceeding 0.1 mol %.

17. Use according to claim 10, wherein the compound 1-Ru is added to the reaction mixture in solid portions and/or continuously using a pump as a solution in an organic solvent.

18. Use according to claim 10, wherein the gaseous reaction by-product, selected from ethylene, propylene, butylene, is actively removed from the reaction mixture using an inert gas barbotage or by means of a vacuum.

Description

[0067] The subject of the invention is explained in embodiments in the Figures, in which:

[0068] FIG. 1 presents the structure of the Ru17a compound obtained on the basis of X-ray structural analysis;

[0069] FIG. 2 presents a summary of precatalysts and catalysts of olefin metathesis available on the market, and of novel precatalysts and catalysts according to the invention;

[0070] FIG. 3 presents a photography showing: (A) the set up and closed reaction systemautoclave, and (B) the reaction system (autoclave), which is open prior to the ethenolysis reaction and does not require a glovebox at any stage of the reaction process.

[0071] In this description, terms used have the following meanings.

[0072] Terms undefined in this document have meanings which are provided and understood by the specialist in the field in light of the best knowledge available, this disclosure and the context of the patent application description.

[0073] Unless otherwise stated, the following conventions of chemical terms are used in this description and have the meanings indicated as in the definitions below:

[0074] As used in this description, the term halogen atom means an element selected from F, Cl, Br, I.

[0075] The term carbene means an electrically inert molecule in which the carbon atom has two non-bonding electrons occurring in the singlet or triplet state and is linked by a single covalent bond to two groups or linked by a double covalent bond to one group. The term carbene also includes carbene analogues in which the carbene carbon atom is replaced by another chemical element such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulfur, selenium or tellurium.

[0076] The term alkyl refers to a saturated, linear or branched hydrocarbon substituent with the indicated number of carbon atoms. Examples of alkyl substituents include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n-decyl. Representative branched (C.sub.1-C.sub.10) alkyls include -isopropyl, -sec-butyl, -isobutyl, -tertbutyl, -isopentyl, -neopentyl, -1-methylbutyl, -2-methylbutyl, -3-methylbutyl, -1,1-dimethylpropyl, -1,2-dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -3-methylpentyl, -4-methylpentyl, -1-ethylbutyl, -2-ethylbutyl, -1,1-dimethylbutyl, -1,2-dimethylbutyl, -1,3-dimethylbutyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3,3-dimethylbutyl, -1-methylhexyl, -2-methylhexyl, -3-methylhexyl, -4-methylhexyl, -1,2-dimethylpentyl, -1,3-dimethylpentyl, -5-methylhexyl, -1,2-dimethylhexyl, -1,3-dimethylhexyl, -3,3-dimethylhexyl, -1,2-dimethylheptyl, -1,3-dimethylheptyl, -3,3-dimethylheptyl and the like.

[0077] The term alkoxyl refers to an alkyl substituent as defined above, connected via an oxygen atom.

[0078] The term perfluoroalkyl denotes an alkyl group as defined above, in which all the hydrogen atoms have been replaced with the same or different halogen atoms.

[0079] The term cycloalkyl refers to a saturated, mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms. Examples of cycloalkyl substituent include -cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl and the like.

[0080] The term alkenyl refers to an unsaturated, linear or branched, acyclic hydrocarbon substituent with the indicated number of hydrogen atoms and containing at least one double carbon-carbon bond. Examples of alkenyl substituents include -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1-butenyl, -2-methyl-2-butenyl, -2,3-dimethyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-nonenyl, -1-decenyl, -2-decenyl, -3-decenyl and the like.

[0081] The term cycloalkenyl refers to an unsaturated, cyclic or branched, cyclic hydrocarbon substituent with the indicated number of hydrogen atoms and containing at least one double carbon-carbon bond. Examples of cycloalkenyl substituents

include -cyclopropene, -cyclobutene, -cyclopentene, -cyclohexene, -cycloheptene, -cyclooctene, -cyclononene, -cyclodecene, -metylcyclopropene, -ethylcyclobutene, -isopropylcyclo pentene, -methylcyclohexene and the like.

[0082] The term aryl refers to an aromatic, mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms. Examples of aryl substituents

include -phenyl, -tolyl, -xylyl, -naphthtyl, -2,4,6-trimethylphenyl, -2-fluorophenyl, -4-fluorophenyl, -2,4,6-trifluorophenyl, -2,6-difluorophenyl, -4-nitrophenyl and the like.

[0083] The term aralkyl refers to an alkyl substituent as defined above, substituted with at least one aryl as defined above. Examples of aralkyl substituents include -benzyl, -diphenylmethyl, -triphenylmethyl and the like.

[0084] The term heteroaryl refers to an aromatic mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms, in which at least one carbon atom has been replaced with a heteroatom selected from O, N and S atoms. Examples of heteroaryl substituents include -furyl, -thienyl, -imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, -oxadiazolyl, -thiadiazolyl, -tetrazolyl, -pyridyl, -pyrimidyl, -triazinyl, -indolyl, -benzo[b]furyl, -benzo[b]thienyl, -indazolyl, -benzoimidazolyl, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl and the like.

[0085] The term heterocycle refers to a saturated, unsaturated or partially unsaturated hydrocarbon substituent, with the indicated number of carbon atoms, in which at least one carbon atom has been replaced with a heteroatom selected from O, N and S atoms. Example heterocycle substituents include -furyl, -thiophenyl, -pyrrolyl, -oxazolyl, -imidazolyl, -thiazolyl, -isoxazolyl, -pyrazolyl, -isothiazolyl, -triazinyl, -pyrrolidinonyl, -pyrrolidinyl, -hydantoinyl, -oxiranyl, -oxetanyl, -tetrahydrofuranyl, -tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl, -chromonyl, -coumarinyl, -indolyl, -indolysinyl, -benzo[b]furanyl, -benzo[b]thiophenyl, -indazolyl, -purinyl, -4H-quinolysinyl, -isoquinolyl, -quinolyl, -phtalazinyl, -naphtyridinyl, -carbazolyl, --carbolinyl and the like.

[0086] The term neutral ligand refers to an non-charged substituent capable of coordinating with a metallic center (transition metal atom). Examples of such ligands may include: N-heterocyclic carbenes (NHC), cyclic (alkyl) (amino) carbenes (CAAC), amines, phosphines and their oxides, alkyl and aryl phosphites and phosphates, arsines and their oxides, ethers, alkyl and aryl sulfides, coordinated unsaturated or aromatic hydrocarbons, alkyl and aryl halides, nitriles, isonitriles, sulfides, sulfoxides, sulfones, thioketones, thioamides, thioester, thionoesters and dithioesters.

[0087] The term anionic ligand refers to a substituent capable of coordinating with a charged metallic center (transition metal atom), which can partially or fully compensate the charge of the metallic center. Examples of such ligands may include fluoride, chloride, bromide, iodide, cyanide, cyanate and thiocyanate anions, carboxylic acid anions, alcohol anions, phenol anions, thiol and thiophenol anions, anions of hydrocarbons with delocalized charge (e.g. cyclopentadiene anion), anions of (organo)sulfuric acids and (organo)phosphoric acids and their esters (such as e.g. anions of alkylsulfonic and arylsulfonic acids, anions of alkylphosphoric and arylphosphoric acids, anions of alkyl and aryl esters of sulfuric acid, anions of alkyl and aryl esters of phosphoric acids, anions of alkyl and aryl esters of alkylphosphoric and arylphosphoric acids).

[0088] The term heteroatom means an atom selected from the group comprising oxygen sulfur, nitrogen, phosphorous, boron, silicon, arsenic, selenium, tellurium.

[0089] The term PAO stands for polyolefins, an abbreviation for Poly-Alpha-Olefins, in the case of the present invention, an abbreviation used for low molecular weight polyolefins used as high boiling point solvents. It also denotes a class of solvents and/or lubricants that are the product of the polymerization of ethylene derivatives, leading to the formation of branched, saturated hydrocarbons, used here as heat-resistant, non-polar, high boiling point solvents.

EMBODIMENTS OF THE INVENTION

[0090] The following examples are included only to illustrate the invention and to clarify particular aspects of the invention, not to limit it, and should not be equated with the entire scope of the invention as defined in the appended claims. In the following examples, unless otherwise indicated, standard materials and methods used in the field were used or followed manufacturers' recommendations for specific reactants and methods.

[0091] When necessary, model compounds for the metathesis reaction were purified by fractional distillation and then stored under inert gas atmosphere over activated neutral aluminum oxide. Tetrahydrofuran was purified by sodium-potassium alloy distillation in the presence of benzophenone, and then stored over 4 molecular sieves. When expedient, selected reactions were carried out under an argon atmosphere using reaction vessels heated at 130 C. Aluminum oxide (Al.sub.2O.sub.3, neutral, Brockman Grade I) was activated by heating at 150 C. under reduced pressure for 16 hours.

[0092] Starting compounds for the synthesis of aldehyde derivatives were commercially available.

Example I

Synthesis of New Aldehydes, Precursors of CAAC Ligands

[0093] The following Scheme 9 illustrates the first three steps in the synthesis of CAAC ligand precursors to synthesize ruthenium catalysts for olefin metathesis (with the general formulae Ru1a to Ru21a, Scheme 9), which are the subject of the present invention.

##STR00023##

[0094] Reactions R1 through R5, shown in Scheme 9, were carried out using commercially available substrates based on procedures described in the literature with modifications developed by the authors of the invention. Unless otherwise written, the reactions described used commercially available solvents and paid no attention to the presence of oxygen and/or moisture.

Reaction R1

[0095] In the R1 step (Scheme 9), the synthesis of an epoxide with the general formula BX is carried out. For this purpose, a ketone of the general formula AX and a trimethyl sulfonyl salt, preferably either trimethyl sulfonyl bromide (Me.sub.3SBr) or iodide (Me.sub.3SI), are used. The transformation is carried out in an organic solvent, preferably acetonitrile (MeCN) or another organic solvent, using a stoichiometric amount of the sulfonium salt and using a metal hydroxide, preferably potassium hydroxide (KOH). The reaction mixture is carried out at an elevated temperature, preferably 60 C. for 2 to 16 hours. The product is separated by filtration from the reaction mixture and distillation of the solvent.

Embodiment of R1

##STR00024##

[0096] Into a reaction vessel equipped with a stirring element, 2-acetylthiophene (7.01 g, 6.00 mL, 55.0 mmol, 1.0 equiv.), Me.sub.3SI (14.9 g, 71.5 mmol, 1.3 equiv.), KOH (9.44 g, 0.14 mmol, 2.6 equiv.), distilled water (0.25 mL) and MeCN (55 mL) were placed under an argon atmosphere. The contents of the vessel were stirred for 16 hours at 60 C. After the reaction was completed, 15 mL of diethyl ether (Et.sub.2O) was added, the precipitate was filtered off and washed again with diethyl ether (40 mL), the solvent was evaporated under reduced pressure. The remaining dark pink oil was washed with diethyl ether (40 mL), the solvent was evaporated and washed with n-hexane (40 mL), the solvent was evaporated under reduced pressure to give the expected product as a yellow oil in 91% yield (6.98 g, 49.8 mmol).

[0097] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.21 (dd, J=5.1, 1.2 Hz, 1H), 7.04 (dd, J=3.7, 1.3 Hz, 1H), 6.96 (dd, J=5.1, 3.6 Hz, 1H), 3.07-3.03 (m, 2H), 1.78-1.78 (m, 3H);

[0098] .sup.13C NMR (101 MHz, CDCl.sub.3) ppm: 145.9, 127.2, 125.0, 124.8, 58.7, 55.2, 22.2;

Reaction R2

[0099] In step R2 (Scheme 9), the synthesis of an aldehyde of the general formula CX is carried out. For this purpose, an epoxide of the general formula BX and Lewis acid, preferably SiO.sub.2, chloroform, ZnCl.sub.2 or ZnBr.sub.2 are used. The transformation is carried out in an organic solvent, preferably ethyl acetate (EtOAc), chloroform or toluene (PhMe). The reaction mixture is carried out at room temperature until full conversion of the substrate (2.5-48 hours). The product is purified by distillation of the solvent and then used in the next step without further purification.

Embodiment of Performing Reaction R2

##STR00025##

[0100] 2-Methyl-2-(thiophen-2-yl)epoxide (6.6 g, 47.0 mmol, 1.0 equiv.), silicon oxide (3.76 g) and EtOAc (90 mL) were placed in a reaction vessel equipped with a stirring element. The reaction was carried out for 2.5 hours at room temperature. Silicon oxide was filtered off and solvent was distilled off under reduced pressure, to give the expected product as a yellow oil in 69% yield (2.60 g, 18.5 mmol).

Alternative Embodiment of Performing Reaction R2

##STR00026##

[0101] 2-Methyl-2-(thiophen-2-yl)epoxide (6.6 g, 47.0 mmol, 1.0 equiv.) and chloroform (60 mL) were placed in a reaction vessel equipped with a stirring element. The reaction was carried out for 2 hours at room temperature. The solvent was distilled off under reduced pressure to give the expected product as a yellow oil in >99% yield (6.59 g, 47.0 mmol).

Alternative Embodiment of Performing Reaction R2

##STR00027##

[0102] 2-Methyl-2-(benzothiophen-2-yl)epoxide (5.32 g, 28.0 mmol, 1 equiv.), zinc chloride (3.81 g, 28.0 mmol, 1 equiv.) and toluene (119 mL) were placed in a reaction vessel equipped with a stirring element. The reaction was carried out for 2 hours at room temperature. The reaction mixture was filtered off on a Schott funnel, the solvent was distilled off under reduced pressure, and the crude product was sublimed under reduced pressure using a Kugelrohr glass oven, to give the expected product as a colorless solid in 97% yield (5.17 g, 27.2 mmol).

Reaction R3

[0103] In step R3 (Scheme 9), the synthesis of an aldehyde with the general formula FX is carried out. For this purpose, an aldehyde of the general formula CX and an alkenyl halide, preferably chloride, a metal hydroxide, preferably NaOH, a quaternary ammonium salt, preferably tetra-N-butylammonium bromide, are used. The transformation is carried out in an organic solvent, preferably toluene. The reaction mixture is carried out at an elevated temperature, preferably 40-60 C. for 30 minutes to 5 hours. The product is separated by extraction from the reaction mixture. It is then dried over a drying agent, preferably sodium sulfate or magnesium sulfate, solid is filtered off, and the solvent is distilled off under reduced pressure. The product is used in the next step without additional purification.

Embodiment of Performing Reaction R3

##STR00028##

[0104] Into a reaction vessel equipped with a stirring element were placed thiophene-2-ylpropanal (6.4 g, 46.0 mmol, 1.00 equiv.), 3-chloro-2-methylpropene (5.1 g, 55.0 mmol, 1.20 equiv.), potassium hydroxide (2.7 g, 69.0 mmol, 1.50 equiv.), tetrabutylammonium bromide (0.6 g, 1.8 mmol, 0.04 equiv.), toluene (60 mL) and water (3 mL). The reaction was carried out for 3 hours at 60 C. The mixture was cooled to room temperature, 15 mL of water was added and extracted with toluene (425 mL), dried over sodium sulfate. The drying agent was filtered off and the solvent was distilled off under reduced pressure, to give the expected product as a yellow oil in 68% yield (7.3 g, 31.0 mmol).

TABLE-US-00001 TABLE 1 The obtained aldehydes .sup.1H NMR (ppm) Molar mass CHO Structure/Number Molecular formula [g/mol] (solvent) [00029] C.sub.7H.sub.8OS 140.21 9.64 (d, J = 1.7 Hz) (CHCl.sub.3) C1 [00030] C.sub.7H.sub.8OS 140.21 9.55 (d, J = 1.8 Hz) (CHCl.sub.3) C2 [00031] C.sub.8H.sub.10OS 154.23 9.64 (d, J = 3.5 Hz), 9.61 (d, J = 2.4 Hz, 3H) (CHCl.sub.3) C3 [00032] C.sub.11H.sub.10OS 190.27 9.73 (d, J = 1.6 Hz) (CHCl.sub.3) C4 [00033] C.sub.11H.sub.10O.sub.2 174.20 9.76 (d, J = 1.4 Hz) (CD.sub.2Cl.sub.2) C5 [00034] C.sub.11H.sub.14OS 194.30 9.52 (s) (CDCl.sub.3) F6 [00035] C.sub.11H.sub.14OS 194.30 9.52 (s) (CDCl.sub.3) F7 [00036] C.sub.12H.sub.16OS 208.32 9.50 (s) (CDCl.sub.3) F8 [00037] C.sub.15H.sub.16OS 244.36 9.61 (s) (CDCl.sub.3) F9 [00038] C.sub.15H.sub.16O.sub.2 228.29 9.67 (s) (CD.sub.2Cl.sub.2) F10

Reaction R4

[0105] In step R4 (Scheme 9), the synthesis of an enol ether of the general formula EX is carried out. For this purpose, DX ketone and a suitable Wittig reagent, preferably chloride, a strong base, preferably potassium tert-butoxide, are used. The transformation is carried out in an anhydrous organic solvent, preferably tetrahydrofuran. The reaction mixture is carried out in the temperature range 78 C.-RT for 16 hours. Then n-heptane is added to precipitate phosphine oxide. After filtering off solids and distilling off the solvent, the product is separated by column chromatography.

Alternative Embodiment of Performing Reaction R4

##STR00039##

[0106] Wittig's reagent (13.2 g, 38.5 mmol, 1.35 equiv.), potassium tert-butoxide (20.4 g, 38.5 mmol, 1.35 equiv.) and anhydrous tetrahydrofuran (57 mL) were placed in a reaction vessel equipped with a stirring element under an argon atmosphere. The reaction was carried out for one hour at 78 C. The mixture was then warmed to room temperature and allowed to stir vigorously for 30 minutes. The mixture was cooled again to 78 C., after which a solution of acetylferrocene (6.50 g, 28.5 mmol, 1 equiv.) in anhydrous tetrahydrofuran (10 mL) was added dropwise. After 30 minutes, the mixture was warmed to room temperature and the reaction was carried out for 16 hours at this temperature. The solvent was then evaporated under reduced pressure, to the residue n-heptane (250 mL) was added, the phosphine oxide was precipitated and filtered off. The solvent was distilled off under reduced pressure, the crude product was purified by column chromatography (Al.sub.2O.sub.35% H.sub.2O) collecting fractions using eluent from 0 to 20% ethyl acetate in n-hexane. The expected product was obtained as a red-orange oil with a yield of 96% (6.98 g, 27.2 mmol).

[0107] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 6.22-6.20 (m, 0.531H), 5.96-5.94 (m, 0.471H), 4.60-4.56 (m, 0.472H), 4.25-4.22 (m, 0.532H), 4.19-4.16 (m, 0.472H), 4.16-4.14 (m, 0.532H), 4.12 (s, 0.535H), 4.08 (s, 0.475H), 3.65 (s, 0.473H), 3.64 (s, 0.533H), 1.93 (d, J=1.4 Hz, 0.533H), 1.84 (d, J=1.4 Hz, 0.473H).

[0108] .sup.13C NMR (101 MHz, CDCl.sub.3) ppm: 142.8, 141.5, 11.0, 109.3, 87.8, 83.6, 69.1, 68.9, 67.9, 67.7, 67.6, 64.2, 59.9, 59.8, 17.5, 12.8.

Reaction R5

[0109] In step R5 (Scheme 9), the synthesis of an aldehyde of the general formula CX is carried out. For this purpose, an enol ether EX and a suitable inorganic acid, preferably hydrobromic acid, are used. The transformation is carried out in a mixture of organic solventwater, preferably acetonewater (4-1 v/v). The acid is added dropwise at a temperature below 50 C., using a dry ice-acetone cooling bath, and then the mixture is heated to 45 C. and stirred vigorously for another 2 hours until full conversion of the substrate is achieved. Next, a weak base, preferably sodium bicarbonate, is added until a pH of 8 is obtained, the product is extracted with an organic solvent, preferably methylene chloride, then dried over a drying agent, preferably sodium or magnesium sulfate. After filtering off solids and evaporating the solvent under reduced pressure, the product is obtained.

Embodiment of Performing Reaction R5

##STR00040##

[0110] Into a reaction vessel equipped with a stirring element, ether (2.60 g, 10.2 mmol, 1 equiv.), acetone (12 mL) and water (3 mL) were placed. The mixture was cooled below 50 C. and HBr (48% aqueous solution, 2.30 mL, 2 equiv.) was added dropwise under an argon atmosphere. The reaction was then carried out for 2 hours at 45 C. An aqueous solution of NaHCO.sub.3 was added to the reaction mixture until a pH of 8. The product was extracted with methylene chloride, dried over magnesium sulfate, which was then filtered off. The solvent was distilled off under reduced pressure to give the expected product as a maroon oil in 93% yield (2.30 g, 9.50 mmol).

[0111] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 9.72 (d, J=2.2 Hz, 1H), 4.21-4.19 (m, 2H), 4.16 (s, 4H), 4.12-4.09 (m, 2H), 3.26 (qd, J=7.0, 2.3 Hz, 1H), 1.36 (d, J=7.0 Hz, 3H).

[0112] .sup.13C NMR (101 MHz, CDCl.sub.3) ppm: 201.0, 85.0, 68.8, 68.3, 68.3, 67.1, 67.0, 45.7, 14.7.

Example II

Synthesis of CAAC Ligands

[0113] The following Scheme 15 illustrates the synthesis of CAAC ligands allowing the preparation of ruthenium catalysts for olefin metathesis (general formula Ru1a to Ru21a, Scheme 18), which are the subject of the present invention.

[0114] The R6 and R8 reactions shown in Scheme 15 were carried out using commercially available compounds based on procedures described in the literature with modifications developed by the authors. Unless otherwise written, the reactions described used commercially available solvents and paid no attention to the presence of oxygen and/or moisture.

##STR00041##

[0115] In step R6 (Scheme 15), the synthesis of imine HX is carried out, for this purpose a suitable aniline and an aldehyde of the general formula FX are used, in the presence of an acid, preferably p-toluenesulfonic acid (PTSA). The reaction is carried out preferably in toluene or other organic solvent. The reaction mixture is carried out at the boiling point of the solvent. The product is separated by filtration through neutral Al.sub.2O.sub.3 and distillation of the solvent. The product is used in the next step without additional purification.

[0116] In step R7 (Scheme 15), the synthesis of a CAAC ligand of the general formula LX is carried out, for this purpose imine of the general formula HX from step R6 or R9 is used in the presence of an acid, preferably 4 normal hydrochloric acid in dioxane. The reactions are carried out under an argon atmosphere in anhydrous toluene at 85 C. Chloride ions are then exchanged, preferably to tetrafluoroborate ions, and the crude product is precipitated from a mixture of organic solvents, preferably methanol:diethyl ether.

[0117] In step R8 (Scheme 15), the synthesis of imine GX is carried out. For this purpose, a suitable aniline and an aldehyde of the general formula CX are used, in the presence of Lewis acid, preferably titanium(IV) isopropanolate. The reaction is carried out in an anhydrous organic solvent, preferably in methanol or another organic solvent at a temperature in the range of 25-45 C. The product is separated by precipitation and filtration through neutral Celite and distillation of the solvent. The product is used in the next step without additional purification.

[0118] In step R9 (Scheme 15), the synthesis of imine HX is carried out, and for this purpose imine GX, an alkyl halide, preferably a chloride, a base, preferably n-BuLi, and an organic solvent, preferably tetrahydrofuran (THF) or another organic solvent are used. The reaction is carried out at 78 C.-RT for 10 minutes, cooled to 20 C., the alkyl halide is added, then warmed to room temperature and the reaction is carried out for 16 hours. The product is separated by filtration through neutral Celite and distillation of the solvent. The product is used in the next step without additional purification.

Embodiment of Performing Reactions R6-R7

##STR00042##

[0119] In a round-bottom flask equipped with a stirring element, 2,4-dimethyl-2-thiophenylpent-4-enal (2.11 g, 9.00 mmol, 1.00 equiv.), aniline (1.87 g, 9.00 mmol, 1.00 equiv.) and PTSA (17 mg, 0.09 mmol, 1 mol %) dissolved in PhMe (C=0.30 M) were placed. The reaction was carried out at boiling temperature of toluene until the full conversion of the substrates (collecting water in a Dean-Stark apparatus). The solvent was evaporated under reduced pressure, the crude reaction mixture was dissolved in n-hexane, filtered through neutral alumina (Al.sub.2O.sub.3, neutral, Brockman Grade I), washed with a mixture of n-hexane:ethyl acetate (98:2, v/v), and dried under reduced pressure to give imine in 44% yield (1.50 g, 3.94 mmol), which was used in the next step without further purification.

[0120] The imine from the previous step, 4 M HCl (solution in dioxane, 2.53 g, 2.46 mL, 9.83 mmol, 2.5 equiv.) and anhydrous PhMe (C=0.50 M) were placed in a round-bottom flask under an argon atmosphere. The reaction was carried out for 16 hours at 85 C. The solvent was evaporated under reduced pressure. The crude product was dissolved in a methylene chloride water mixture, NaBF.sub.4 (0.86 g, 7.86 mmol, 2.0 equiv.) was added and ion exchange was carried out for 2 h. The organic fraction was collected, washed with water and dried over sodium sulfate. The product was precipitated from the MeOH:Et.sub.2O mixture, to give final product as a colorless crystals in 39% yield (0.72 g, 1.53 mmol).

[0121] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.62-9.55 (m, 1H), 8.94 (s, 1H), 7.68-7.62 (m, 1H), 7.56-7.47 (m, 3H), 7.39-7.31 (m, 5H), 7.29-7.27 (m, 1H), 7.16-7.07 (m, 2H), 6.71-6.61 (m, 1H), 3.08 (dd, J=23.3, 13.9 Hz, 2H), 2.72 (dd, J=54.9, 14.0 Hz, 2H), 2.16 (s, 3H), 1.95 (s, 3H), 1.85 (s, 3H), 1.57-1.52 (m, 5H), 1.45 (s, 4H), 1.34 (s, 5H), 1.27 (s, 4H), 1.17 (s, 5H).

[0122] .sup.13C NMR (101 MHz, CDCl.sub.3): 184.9, 184.5, 151.0, 150.5, 142.2, 142.0, 142.0, 141.2, 132.1, 131.0, 130.7, 130.6, 129.2, 128.9, 128.6, 127.0, 126.6, 126.3, 125.5, 125.5, 123.1, 82.5, 82.5, 81.9, 81.9, 52.6, 52.4, 50.5, 49.2, 37.7, 37.1, 34.7, 34.5, 33.8, 33.7, 31.0, 30.9, 30.7, 29.4, 29.0, 28.9, 27.2, 26.6.

Embodiment of Carrying Out Reactions R8-R9-R7

##STR00043##

[0123] In a round-bottomed flask under an argon atmosphere, 2-ferrocenylpropanal (5.45 g, 22.5 mmol, 1.00 equiv.) and anhydrous methanol (150 mL) were placed, followed by the addition of titanium(IV) isopropanolate (13.3 mL, 45 mmol, 2.00 equiv.). To the reaction mixture thus prepared, 2,6-diethylaniline (4.27 mL, 25.8 mmol, 1.15 equiv.) was added dropwise. The reaction was carried out for 16 h at 45 C. The solvent was evaporated under reduced pressure. The crude product was dissolved in n-pentane and then filtered through neutral Celite. The solvent was evaporated to give the crude product as a maroon oily liquid in 73% yield (6.15 g, 16.5 mmol).

[0124] Imine (6.36 g, 17.1 mmol, 1.00 equiv.) and anhydrous tetrahydrofuran (8.55 mL) were placed in a round-bottom flaskpreviously heated under reduced pressureunder an argon atmosphere. The mixture was then cooled to 78 C. in a dry iceacetone cooling bath. A solution of n-BuLi (2.35 M solution in n-hexane, 8.72 mL, 20.5 mmol, 1.20 equiv.) was then added dropwise with intense stirring, followed by warming to room temperature. After one hour, the reaction mixture was cooled again to 78 C. in a dry ice-acetone cooling bath and 3-chloro-2-methylpropene (2.50 mL, 25.6 mmol, 1.50 eqn.) was added dropwise. The reaction was carried out for 16 h at room temperature. The solvent was evaporated under reduced pressure. The crude product was purified by distillation to give a maroon oily liquid in 100% yield (7.30 g, 17.1 mmol).

[0125] The imine from the previous step (7.30 g, 17.1 mmol, 1 equiv.) dissolved in anhydrous PhMe (C=500 mM) was placed in a round-bottom flask under an argon atmosphere. The mixture was cooled to 78 C. in a dry ice-acetone cooling bath. HCl solution (4 M solution in dioxane, 12.8 mL, 51.2 mmol, 3 equiv.) was then added dropwise and the reaction was carried out for 16 h at 85 C. with vigorous stirring. The solvent was evaporated under reduced pressure. The crude product was dissolved in methylene chloride (about 10 mL), a saturated aqueous solution of NaBF.sub.4 (3.75 g, 34.1 mmol, 2 equiv.) was added and the ion exchange was carried out for 2 h with vigorous stirring. The mixture was extracted three times with methylene chloride, dried with anhydrous magnesium sulfate and filtered through neutral Celite, after which the solvent was evaporated under reduced pressure. The product was precipitated from the DCM:Et.sub.2O mixture to give red crystals in 47% yield (4.14 g, 8.05 mmol).

TABLE-US-00002 TABLE 2 Summary of CAAC ligands obtained according to the general procedure from Example III. Structure/Number Selected analytical data [00044] L1 .sup.1H NMR (400 MHz, CDCl.sub.3): ppm 9.53-9.44 (m, 0.53 1H), 9.39-9.27 (m, 0.4 1H), 9.25-9.17 (m, 0.07 1H) .sup.13C NMR (101 MHz, CDCl.sub.3): ppm: 186.5, 145.1, 144.8, 134.2, 133.5, 131.7, 131.7, 130.4, 130.3, 130.2, 129.3, 129.1, 129.1, 127.3, 127.0, 126.9, 126.5, 126.4, 126.0, 125.5, 125.1, 84.3, 83.9, 52.8, 52.8, 50.4, 30.1, 29.5, 29.1, 29.0, 29.0, 28.2, 27.9, 27.7, 27.2, 26.1, 26.0, 22.2, 21.9, 19.7, 19.7, 19.2, 18.9, 15.4 [00045] L2 .sup.1H NMR (400 MHz, CDCl.sub.3): ppm 9.62-9.55 (m, 1H), 8.94 (s, 1H), 7.68-7.62 (m, 1H), 7.56-7.47 (m, 3H), 7.39-7.31 (m, 5H), 7.29-7.27 (m, 1H), 7.16-7.07 (m, 2H), 6.71-6.61 (m, 1H), 3.08 (dd, J = 23.3, 13.9 Hz, 2H), 2.72 (dd, J = 54.9, 14.0 Hz, 2H), 2.16 (s, 3H), 1.95 (s, 3H), 1.85 (s, 3H), 1.57-1.52 (m, 5H), 1.45 (s, 4H), 1.34 (s, 5H), 1.27 (s, 4H), 1.17 (s, 5H); .sup.13C NMR (101 MHz, CDCl.sub.3): ppm: 184.9, 184.5, 151.0, 150.5, 142.2, 142.0, 142.0, 141.2, 132.1, 131.0, 130.7, 130.6, 129.2, 128.9, 128.6, 127.0, 126.6, 126.3, 125.5, 125.5, 123.1, 82.5, 82.5, 81.9, 81.9, 52.6, 52.4, 50.5, 49.2, 37.7, 37.1, 34.7, 34.5, 33.8, 33.7, 31.0, 30.9, 30.7, 29.4, 29.0, 28.9, 27.2, 26.6 [00046] L3 .sup.1H NMR (400 MHz, CDCl.sub.3): ppm 9.22 (s, 0.20 1H), 9.13 (s, 0.28 1H), 9.11 (s, 0.22 1H), 9.05 (s, 0.30 1H) .sup.13C NMR (101 MHz, CDCl.sub.3): 186.5, 186.3, 186.1, 144.6, 144.5, 143.7, 143.6, 142.4, 142.3, 142.0, 141.9, 141.8, 141.8, 141.6, 133.7, 133.6, 133.2, 133.1, 131.0, 130.9, 130.9, 130.9, 129.2, 129.1, 129.0, 128.5, 128.1, 128.0, 127.4, 127.2, 127.1, 127.1, 126.4, 126.3, 126.3, 126.0, 126.0, 126.0, 125.9, 84.6, 84.2, 83.7, 83.6, 52.6, 52.6, 52.6, 52.5, 50.4, 50.2, 50.1, 50.0, 36.8, 36.8, 36.1, 36.0, 33.4, 33.3, 29.1, 29.0, 29.0, 28.9, 28.8, 28.3, 28.1, 27.9, 27.9, 27.5, 27.5, 27.4, 26.6, 22.6, 22.5, 21.3, 21.3, 21.3, 20.0, 20.0, 19.6, 19.5, 19.2, 19.1, 12.7, 12.5, 12.3, 11.8 [00047] L4 .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 9.29 (s, 0.5 1H), 9.24 (s, 0.5 1H), 7.56-7.44 (m, 3H), 7.41-7.37 (m, 0.5 1H), 7.35-7.32 (m, 0.5 1H), 7.31-7.23 (m, 2H), 3.16 (d, J = 14.0 Hz, 0.5 1H), 3.12 (d, J = 14.1 Hz, 0.5 1H), 2.75-2.62 (m, 0.5 1H), 2.69 (d, J = 14.1 Hz, 0.5 1H), 2.66 (d, J = 13.9 Hz, 0.5 1H), 2.34 (s, 0.5 3H), 2.41-2.26 (m, 0.5 1H), 2.07 (s, 0.5 3H), 1.95 (s, 0.5 3H), 1.89 (s, 0.5 3H), 1.62 (s, 0.5 3H), 1.57 (s, 0.5 3H), 1.45 (s, 0.5 3H), 1.42 (s, 0.5 3H), 1.40 (d, J = 6.7 Hz, 0.5 3H), 1.23 (d, J = 6.7 Hz, 0.5 3H), 1.15 (d, J = 6.7 Hz, 0.5 3H), 0.95 (d, J = 6.8 Hz, 0.5 3H) .sup.13C NMR (101 MHz, CDCl.sub.2): 187.9, 145.2, 145.1, 140.2, 139.9, 134.3, 133.9, 132.0, 132.0, 131.0, 130.6, 130.5, 129.1, 129.0, 125.8, 125.7, 125.7, 125.7, 122.9, 122.8, 85.0, 84.6, 53.4, 53.4, 49.2, 49.0, 30.4, 29.8, 28.7, 28.6, 28.1, 27.9, 27.6, 27.1, 26.1, 26.0, 22.1, 22.1, 19.8, 19.4 [00048] L5 .sup.1H NMR (400 MHz, CDCl.sub.3): 9.58 (s, 0.57 1H), 9.10 (s, 0.43 1H), 7.63 (d, J = 8.7 Hz, 0.57 1H), 7.55-7.47 (m, 2H), 7.46- 7.40 (m, 1H), 7.38 (dd, J = 3.0, 1.5 Hz, 0.43 1H), 7.30 (dd, J = 5.1, 1.5 Hz, 0.57 1H), 7.27 (dd, J = 5.0, 1.6 Hz, 0.43 1H), 7.22 (d, J = 2.0 Hz, 0.43 1H), 6.63 (d, J = 2.1 Hz, 0.57 1H), 3.24 (d, J = 14.0 Hz, 0.57 1H), 3.07 (d, J = 13.8 Hz, 0.43 1H), 2.75 (d, J = 13.7 Hz, 0.43 1H), 2.53 (d, J = 14.0 Hz, 0.57 1H), 2.01 (s, 0.43 3H), 1.83 (s, 0.43 3H), 1.82 (s, 0.57 3H), 1.52 (s, 0.43 3H), 1.51 (s, 0.57 3H), 1.44 (s, 0.57 3H), 1.42 (s, 0.57 9H), 1.32 (s, 0.43 9H), 1.25 (s, 0.57 9H), 1.12 (s, 0.43 9H) .sup.13C NMR (101 MHz, CDCl.sub.3): 186.1, 185.6, 150.8, 150.4, 141.9, 141.3, 139.5, 139.2, 132.0, 131.1, 130.9, 130.8, 128.8, 128.5, 128.4, 128.4, 125.8, 125.5, 125.0, 123.1, 122.5, 122.3, 82.5, 81.9, 52.9, 52.7, 48.7, 47.6, 37.6, 37.1, 34.6, 34.5, 33.7, 33.6, 30.9, 30.9, 30.7, 28.7, 28.4, 27.8, 27.0, 26.2 [00049] L6 .sup.1H NMR (400 MHz, CDCl.sub.3): 9.38 (s, 0.23 1H), 9.31 (s, 0.27 1H), 9.28 (s, 0.23 1H), 9.22 (s, 0.23 1H), 7.60 (m, 0.23 1H + 0.27 1H), 7.49 (m, 0.23 1H + 0.27 1H), 7.45-7.40 (m, 1H), 7.34- 7.26 (m, 1H), 7.04-6.98 (m, 1H), 6.98-6.89 (m, 1H), 3.23 (d, J = 13.9 Hz, 0.27 1H), 3.23 (d, J = 14.3 Hz, 0.27 1H), 3.22 (d, J = 14.2 Hz, 0.23 1H), 3.18 (d, J = 14.2 Hz, 0.23 1H), 2.67 (d, J = 14.2 Hz, 0.27 1H), 2.63 (d, J = 14.1 Hz, 0.23 1H), 2.60 (d, J = 14.2 Hz, 0.27 1H), 2.60 (d, J = 14.1 Hz, 0.23 1H), 2.39-1.19 (m, 18H), 1.32 (d, J = 6.7 Hz, 0.27 3H), 1.16 (d, J = 6.7 Hz, 0.27 3H), 1.11 (d, J = 6.7 Hz, 0.23 3H), 1.01 (t, J = 7.4 Hz, 0.23 3H), 0.85 (d, J = 6.7 Hz, 0.23 3H), 0.78 (t, J = 7.4 Hz, 0.27 3H), 0.70 (t, J = 7.4 Hz, 0.23 3H), 0.45 (t, J = 7.4 Hz, 0.27 3H) .sup.13C NMR (101 MHz, CDCl.sub.3): 188.0, 188.0, 187.9, 187.5, 144.5, 144.3, 143.6, 143.5, 141.8, 141.7, 141.6, 141.5, 139.5, 139.5, 139.3, 139.3, 133.6, 133.5, 133.1, 132.9, 130.9, 130.9, 130.8, 130.7, 128.8, 128.7, 128.5, 128.4, 128.4, 128.3, 128.2, 126.1, 126.1, 126.0, 126.0, 125.8, 125.6, 125.6, 125.6, 122.8, 122.7, 122.6, 84.4, 84.1, 83.7, 83.6, 53.0, 52.9, 52.9, 48.7, 48.5, 48.1, 47.9, 36.8, 36.8, 36.1, 35.8, 33.3, 33.3, 28.9, 28.9, 28.7, 28.7, 28.5, 28.4, 28.4, 28.1, 27.4, 27.2, 27.1, 27.1, 27.0, 25.8, 22.5, 22.4, 21.3, 21.3, 21.3, 19.9, 19.8, 19.6, 19.4, 19.0, 18.9, 12.6, 12.5, 12.2, 11.9 [00050] L7 .sup.1H NMR (400 MHz, CDCl.sub.3): 9.44 (s, 0.5 1H), 9.33 (s, 0.5 1H), 7.48 (dd, J = 3.7, 1.1 Hz, 0.5 1H), 7.46-7.31 (m, 3H), 7.25-7.20 (m, 1H), 7.19-7.15 (m, 0.5 1H), 7.14-7.10 (m, 1H), 3.05 (d, J = 14.3 Hz, 1H), 2.79-2.63 (m, 1h + 0.5 1H), 2.54-2.42 (m, 0.5 1H), 2.42-2.13 (m, 0.5 3H + 2H), 2.00 (s, 0.5 3H), 1.60 (d, J = 18.8 Hz, 3H), 1.47 (d, J = 8.3 Hz, 3H), 1.37 (d, J = 6.7 Hz, 0.5 3H), 1.16 (dd, J = 8.5, 6.7 Hz, 3H), 1.02 (td, J = 7.4, 2.7 Hz, 3H), 0.87 (d, J = 6.7 Hz, 0.5 3H); .sup.13C NMR (101 MHz, CDCl.sub.3): 186.4, 186.0, 144.9, 144.9, 140.4, 140.2, 134.1, 133.6, 131.7, 131.6, 130.5, 130.4, 130.2, 130.1, 129.4, 129.3, 127.8, 127.7, 126.3, 125.8, 125.2, 125.1, 84.0, 83.5, 57.6, 57.5, 46.9, 46.3, 35.3, 34.4, 30.2, 29.1, 28.7, 27.7, 27.5, 26.8, 26.0, 25.9, 22.0, 22.0, 19.8, 18.9, 8.7 [00051] L8 .sup.1H NMR (400 MHz, CDCl.sub.3): 9.71 (s, 0H), 9.59 (s, 0H), 9.35 (s, 0H), 9.01 (s, 0H), 7.66-7.47 (m, 1H), 7.43-7.26 (m, 1H), 7.16- 7.10 (m, 0H), 6.63-6.55 (m, 0H), 3.08 (d, J = 14.0 Hz, 0H), 2.96- 2.79 (m, 0H), 2.69-2.52 (m, 0H), 2.50-2.25 (m, 0H), 2.07-1.94 (m, 0H), 1.81 (s, 1H), 1.55 (d, J = 4.1 Hz, 1H), 1.49 (s, 1H), 1.44 (s, 2H), 1.33 (s, 1H), 1.25 (s, 2H), 1.11 (s, 2H), 0.92 (td, J = 7.3, 2.4 Hz, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3): 184.1, 150.8, 150.4, 141.9, 141.4, 139.9, 139.1, 132.0, 131.1, 130.7, 129.3, 129.1, 128.8, 128.6, 127.7, 127.5, 126.3, 125.7, 125.5, 123.3, 82.2, 81.7, 57.2, 57.0, 48.2, 45.1, 37.6, 37.0, 34.7, 34.5, 34.2, 33.7, 33.7, 33.5, 33.1, 33.0, 31.2, 31.0, 30.9, 29.3, 27.2, 26.5, 8.3, 8.2 [00052] L9 .sup.1H NMR (400 MHz, CDCl.sub.3): 9.51-9.46 (m, 0.25 1H), 9.41- 9.36 (m, 0.28 1H), 9.33-9.29 (m, 0.21 1H), 9.27-9.22 (m, 0.26 1H), .sup.13C NMR (101 MHz, CDCl.sub.3): 186.7, 186.4, 186.2, 185.8, 144.9, 144.4, 143.8, 143.7, 141.9, 141.8, 141.8, 141.6, 140.4, 140.3, 140.1, 139.8, 133.7, 133.6, 133.4, 133.3, 131.0, 131.0, 130.9, 130.8, 129.7, 129.5, 129.4, 128.5, 128.4, 128.2, 128.1, 128.0, 128.0, 127.9, 126.2, 126.2, 126.2, 126.1, 125.7, 125.7, 83.9, 83.6, 83.1, 83.0, 57.5, 57.4, 57.3, 57.3, 47.1, 46.9, 46.3, 46.1, 37.1, 36.9, 35.8, 35.8, 35.4, 35.3, 34.3, 33.3, 33.3, 29.8, 29.0, 29.0, 28.9, 28.8, 27.8, 27.6, 27.4, 27.3, 27.3, 26.2, 22.6, 22.2, 21.4, 21.3, 19.8, 19.8, 19.7, 19.7, 18.9, 18.8, 12.6, 12.5, 12.2, 11.9, 8.8, 8.7, 8.7, 8.5 [00053] L10 .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 9.23 (s, 0.5 1H), 9.19 (s, 0.5 1H), 7.93-7.80 (m, 2H), 7.62 (m, 0.5 1H), 7.53-7.47 (m, 0.5 1H + 1H), 7.46-7.38 (m, 2H + 0.5 1H), 7.38-7.34 (m, 0.5 1H), 7.31-7.28 (m, 0.5 1H), 7.27-7.24 (m, 0.5 1H), 3.18 (d, J = 14.3 Hz, 0.5 1H), 3.13 (d, J = 14.2 Hz, 0.5 1H), 2.83 (d, J = 14.2 Hz, 0.5 1H), 2.82 (d, J = 14.2 Hz, 0.5 1H), 2.75-2.57 (m, 1H), 2.35 (s, 0.5 3H), 2.19 (s, 0.5 3H), 2.13 (s, 0.5 3H), 2.07 (s, 0.5 3H), 1.66 (s, 0.5 3H), 1.61 (s, 0.5 3H), 1.56 (s, 0.5 3H), 1.55 (s, 0.5 3H), 1.41 (d, J = 6.7 Hz, 0.5 3H), 1.29 (d, J = 6.7 Hz, 0.5 3H), 1.17 (d, J = 6.8 Hz, 0.5 3H), 1.00 (d, J = 6.7 Hz, 0.5 3H) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 186.5, 186.2, 145.1, 144.9, 143.3, 142.8, 140.3, 140.1, 139.4, 139.2, 134.1, 133.8, 132.1, 132.0, 130.8, 130.7, 130.5, 130.4, 125.9, 125.8, 125.7, 125.6, 125.6, 125.6, 124.8, 124.7, 123.7, 123.3, 122.7, 122.6, 85.3, 84.8, 50.4, 50.2, 30.2, 29.8, 28.6, 28.6, 28.4, 27.7, 27.7, 27.6, 26.2, 26.0, 22.1, 21.9, 19.7, 19.6 [00054] L11 .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 9.48 (s, 0.6 1H), 9.03 (s, 0.4 1zH), 7.92-7.80 (m, 2H), 7.72 (d, J = 8.7 Hz, 0.6 1H), 7.66- 7.55 (m, 1H + 0.4 1H), 7.56 (d, J = 0.7 Hz, 0.6 1H), 7.53 (d, J = 0.7 Hz, 0.4 1H), 7.46-7.35 (m, 2H), 7.22 (d, J = 2.0 Hz, 0.4 1H), 6.78 (d, J = 2.1 Hz, 0.6 1H), 3.22 (d, J = 14.2 Hz, 0.6 1H), 3.17 (d, J = 13.9 Hz, 0.4 1H), 2.87 (d, J = 13.8 Hz, 0.4 1H), 2.69 (d, J = 14.2 Hz, 0.6 1H), 2.17 (s, 0.4 3H), 1.99 (s, 0.6 3H), 1.87 (s, 0.4 3H), 1.60 (s, 3H), 1.56 (s, 0.6 3H), 1.46 (s, 0.6 9H), 1.35 (s, 0.4 9H), 1.28 (s, 0.6 9H), 1.20 (s, 0.4 9H) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 184.4, 184.3, 151.0, 151.0, 143.1, 142.9, 142.1, 141.8, 140.3, 140.1, 139.6, 139.0, 132.4, 131.7, 131.0, 130.9, 129.3, 129.1, 125.7, 125.7, 125.5, 125.5, 125.1, 124.7, 124.7, 124.6, 123.8, 123.4, 123.2, 122.6, 83.6, 82.8, 53.2, 53.2, 50.2, 48.8, 37.8, 37.4, 34.8, 34.7, 33.8, 30.9, 30.9, 30.8, 29.7, 28.7, 28.5, 27.3, 26.5 [00055] L12 .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 9.19 (s, 0.22 1H), 9.13 (s, 0.25 1H), 9.09 (s, 0.53 1H) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 186.5, 186.3, 186.2, 186.2, 144.7, 144.4, 143.8, 143.7, 143.2, 143.1, 142.9, 142.8, 142.6, 142.5, 142.4, 142.3, 140.3, 140.2, 140.1, 139.3, 139.2, 139.2, 133.7, 133.6, 133.5, 133.3, 131.2, 131.1, 131.1, 131.0, 128.9, 128.5, 128.4, 126.6, 126.6, 126.6, 126.5, 125.8, 125.8, 125.8, 125.8, 125.6, 125.6, 125.5, 125.5, 124.8, 124.8, 124.7, 124.6, 123.8, 123.7, 123.7, 123.7, 122.6, 122.6, 122.6, 85.3, 85.0, 84.6, 84.5, 53.3, 53.2, 50.3, 50.1, 50.1, 50.1, 37.0, 37.0, 36.4, 36.4, 33.5, 33.5, 29.2, 29.0, 28.9, 28.7, 28.6, 28.5, 28.4, 28.3, 27.9, 27.9, 27.5, 27.5, 27.4, 27.1, 22.7, 22.6, 21.3, 21.3, 21.3, 20.2, 19.9, 19.7, 19.5, 19.5, 19.4, 12.7, 12.5, 12.2, 12.0 [00056] L13 .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 8.93 (s, 1H), 7.67 (dd, J = 0.8, 1.4 Hz, 0.45 1H), 7.66 (dd, J = 0.7, 1.4 Hz, 0.55 1H), 7.55-7.46 (m, 2H), 7.43-7.35 (m, 3H), 7.34-7.28 (m, 2H), 7.03 (d, J = 0.9 Hz, 0.45 1H), 6.97 (d, J = 0.9 Hz, 0.55 1H), 3.16 (d, J = 14.1 Hz, 0.45 1H), 3.10 (d, J = 14.0 Hz, 0.55 1H), 2.99 (hept, J = 6.7 Hz, 0.55 1H), 2.79-2.66 (m, 0.45 1H), 2.69 (d, J = 14.1 Hz, 0.45 1H), 2.68 (d, J = 14.0 Hz, 0.55 1H), 2.36 (s, 0.55 H), 2.33 (s, 0.45 H), 2.11 (s, 0.55 3H), 2.08 (s, 0.45 H), 1.71 (s, 0.55 3H), 1.69 (s, 0.45 3H), 1.67 (s, 0.55 3H), 1.67 (s, 0.45 3H), 1.41 (d, J = 6.9 Hz, 0.55 3H), 1.41 (d, J = 6.7 Hz, 0.45 3H), 1.16 (d, J = 6.7 Hz, 0.45 3H), 0.96 (d, J = 6.7 Hz, 0.55 3H) ppm .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 186.2, 185.9, 155.8, 155.8, 154.2, 153.6, 145.3, 145.2, 134.2, 134.0, 132.3, 132.2, 131.2, 131.0, 130.7, 128.3, 128.3, 126.2, 126.1, 126.0, 125.7, 124.3, 124.2, 122.5, 122.4, 111.6, 111.4, 106.3, 106.1, 85.8, 85.3, 52.2, 47.7, 47.4, 30.3, 29.8, 29.7, 28.5, 28.4, 27.6, 26.3, 26.2, 23.9, 23.0, 22.3, 22.2, 19.9, 19.6 [00057] L14 .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 9.16 (s, 0.47 1H), 8.84 (s, 0.53 1H), 7.75-7.55 (m, 3H), 7.52 (dq, J = 18.5, 0.9 Hz, 0.47 1H), 7.50 (dq, J = 18.4, 0.9 Hz, 0.53 1H), 7.38 (m, 1H), 7.30 (m, 1H), 7.22 (d, J = 2.1 Hz, 0.53 1H), 7.03 (d, J = 0.9 Hz, 0.47 1H), 6.97 (d, J = 0.9 Hz, 0.53 1H), 6.89 (d, J = 2.1 Hz, 0.47 1H), 3.26 (d, J = 13.9 Hz, 0.47 1H), 3.22 (d, J = 13.7 Hz, 0.53 1H), 2.69 (d, J = 13.9 Hz, 0.53 1H), 2.60 (d, J = 14.1 Hz, 0.47 3H), 2.15 (s, 0.53 3H), 2.00 (s, 0.47 3H), 1.86 (s, 0.53 3H), 1.76 (s, 0.47 3H), 1.64 (s, 0.53 3H), 1.62 (s, 0.47 3H), 1.46 (s, 0.47 9H), 1.35 (s, 0.53 9H), 1.31 (s, 9H) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 184.3, 183.9, 155.8, 155.6, 154.0, 153.3, 151.2, 151.1, 142.2, 142.1, 132.6, 131.9, 131.2, 131.1, 129.6, 129.3, 128.4, 128.3, 126.0, 126.0, 125.5, 124.2, 124.1, 124.0, 122.4, 122.3, 111.7, 111.7, 106.6, 106.2, 84.2, 83.5, 52.0, 51.9, 47.4, 46.6, 38.0, 37.5, 35.0, 34.9, 34.0, 33.9, 31.3, 31.1, 31.0, 30.1, 27.5, 27.3, 24.1, 23.7 [00058] L15 .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 8.87 (s, 0.4 H), 8.82 (s, 0.6 1H), 7.67 (d, J = 7.7 Hz, 1H), 7.48 (d, J = 8.2 Hz, 1H), 7.38 (td, J = 1.4, 7.8 Hz, 1H), 7.31 (td, J = 1.1, 7.5 Hz, 1H), 7.15-7.08 (m, 2H), 6.99 (d, J = 5.3 Hz, 0.6 1H), 6.99 (d, J = 5.3 Hz, 0.4 1H), 3.11 (d, J = 13.9 Hz, 0.6 1H), 3.11 (d, J = 14.2 Hz, 0.4 1H), 2.66 (d, J = 14.0 Hz, 0.6 1H), 2.66 (d, J = 14.0 Hz, 0.4 1H), 2.66-2.52 (m, 1H), 2.38 (s, 0.6 3H), 2.38 (s, 0.4 3H), 2.33 (s, 3H), 2.12 (s, 0.6 3H), 2.12 (s, 0.4 3H), 1.86-1.63 (m, 1H + 3H + 3H), 1.37 (d, J = 6.7 Hz, 0.6 3H), 1.46-1.26 (m, 1H), 1.07 (t, J = 7.4 Hz, 0.4 3H), 0.92 (d, J = 6.6 Hz, 0.4 3H), 0.45 (t, J = 7.4 Hz, 0.6 3H) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 186.2, 186.1, 155.8, 155.6, 154.1, 153.8, 144.9, 143.8, 142.6, 142.5, 133.6, 133.5, 131.2, 131.2, 128.2, 128.2, 126.6, 126.6, 126.0, 124.2, 124.2, 122.4, 111.4, 111.3, 106.4, 106.1, 85.1, 84.8, 51.9, 51.9, 47.5, 47.3, 36.4, 36.2, 33.8, 29.7, 29.3, 29.3, 27.7, 27.3, 23.2, 23.0, 22.7, 21.4, 21.4, 20.6, 19.8, 19.7, 12.7, 11.9 [00059] L16 .sup.1H NMR (400 MHz, CDCl.sub.3): 8.66 (bs, 0.57 H), 8.59 (bs, 0.43 1H), 7.42-7.33 (m, 1H), 7.29 (d, J = 7.6 Hz, 0.57 1H), 7.21 (d, J = 7.7 Hz, 1H), 7.16 (d, J = 7.4 Hz, 0.43 1H), 4.41-4.26 (m, 8H), 4.19-4.12 (m, 1H), 2.84-2.44 (m, 2H + 0.57 2H), 2.37-2.23 (m, 2H 0.43 + 0.57 3H), 2.13 (s, 0.43 3H), 2.05-1.96 (m, 3H), 1.64 (s, 0.57 3H), 1.63 (s, 0.43 3H), 1.56 (s, 0.43 3H), 1.54 (s, 0.57 3H), 1.26 (t, J = 7.3 Hz, 0.43 3H), 1.04 (t, J = 7.3 Hz, 0.57 3H) ppm .sup.13C NMR (101 MHz, CDCl.sub.3): 187.4, 187.4, 140.0, 139.9, 134.1, 133.5, 131.5, 131.5, 131.2, 131.1, 130.3, 129.8, 127.9, 127.8, 89.8, 89.5, 83.9, 83.8, 70.3, 70.3, 69.9, 69.8, 69.4, 69.3, 67.6, 67.2, 66.5, 66.2, 50.8, 50.8, 49.1, 48.9, 29.7, 29.1, 27.9, 27.5, 25.9, 25.6, 25.1, 24.6, 19.6, 19.6, 15.6, 14.8 [00060] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 8.48 (s, 1H), 7.52 (t, J = 7.8 Hz, 1H), 7.39 (d, J = 7.3 Hz, 1H), 7.31 (d, J = 7.7 Hz, 1H), 4.47-4.44 (m, 1H), 4.43-4.40 (m, 1H), 4.36-4.29 (m, 6H), 4.18-4.15 (m, 1H), 2.82 (d, J = 14.1 Hz, 1H), 2.69 (d, J = 14.1 Hz, 1H), 2.64-2.51 (m, 3H), 2.37-2.26 (m, 1H), 2.03 (s, 3H), 1.65 (s, 3H), 1.55 (s, 3H), 1.30 (t, J = 7.5 Hz, 3H), 1.08 (t, J = 7.5 Hz, 3H) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 187.0, 140.3, 140.0, 132.1, 128.5, 128.5, 89.8, 84.3, 70.8, 70.5, 69.7, 67.4, 66.7, 51.2, 49.7, 29.7, 28.0, 25.7, 25.6, 25.2, 15.8, 15.2 L17 [00061] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 8.45 (s, 1H), 7.56 (t, J = 7.8 Hz, 1H), 7.41-7.37 (m, 1H), 7.36-7.31 (m, 1H), 4.47-4.43 (m, 1H), 4.43-4.40 (m, 1H), 4.39-4.36 (m, 1H), 4.34 (s, 5H), 4.20-4.14 (m, 1H), 2.86 (d, J = 14.2 Hz, 1H), 2.77-2.65 (m, 2H), 2.53 (hept, J = 7.4 Hz, 1H), 1.99 (s, 3H), 1.67 (s, 3H), 1.55 (s, 3H), 1.38 (d, J = 6.7 Hz, 3H), 1.32 (d, J = 6.8 Hz, 3H), 1.15 (d, J = 6.8 Hz, 3H), 0.87 (d, J = 6.8 Hz, 3H) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 186.6, 145.1, 144.9, 132.6, 129.0, 126.2, 125.8, 89.9, 84.2, 70.9, 70.5, 69.8, 67.7, 66.7, 51.1, 49.0, 30.2, 30.1, 29.7, 27.8, 26.5, 26.3, 25.5, 22.6, 21.9 L18 [00062] L19 .sup.1H NMR (400 MHz, CDCl.sub.3): 9.13 (s, 0.24 1H), 8.55 (s, 0.76 1H) ppm [00063] L20 .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 8.57 (s, 0.56 1H), 8.41 (s, 0.44 1H), 7.51-7.45 (m, 1H), 7.40-7.36 (m, 0.44 1H), 7.35-7.32 (m, 0.56 1H), 7.30-7.26 (m, 0.56 1H), 7.26-7.22 (m, 0.44 1H), 4.46-4.42 (m, 1H), 4.41-4.36 (m, 1H + 0.44 1H), 4.32 (s, 0.44 5H), 4.32 (s, 0.56 5H), 4.26-4.24 (m, 0.56 1H), 4.22-4.19 (m, 0.44 1H), 4.17-4.15 (m, 0.56 1H), 2.86 (d, J = 14.2 Hz, 0.44 1H), 2.78 (d, J = 14.1 Hz, 0.56 1H), 2.75-2.65 (m, 1H + 0.44 1H), 2.59 (hept, J = 6.9 Hz, 0.56 1H), 2.33 (s, 0.56 3H), 2.16 (s, 0.44 3H), 2.01 (s, 0.56 3H), 1.99 (s, 0.44 3H), 1.67 (s, 0.56 3H), 1.65 (s, 0.44 3H), 1.59 (s, 0.44 3H), 1.55 (s, 0.56 3H), 1.39 (d, J = 6.7 Hz, 0.44 3H), 1.34 (d, J = 6.8 Hz, 0.56 3H), 1.13 (d, J = 6.8 Hz, 0.44 3H), 0.89 (d, J = 6.8 Hz, 0.56 3H) .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 187.4, 186.8, 145.2, 145.2, 134.2, 134.1, 132.1, 132.0, 131.0, 130.8, 130.7, 130.5, 126.0, 125.5, 90.2, 89.7, 84.6, 84.4, 70.6, 70.6, 70.5, 70.3, 69.7, 69.7, 67.6, 67.1, 67.0, 66.5, 51.2, 51.1, 49.6, 49.2, 30.1, 30.1, 30.0, 29.1, 28.4, 27.8, 26.4, 26.2, 25.8, 25.3, 22.5, 21.9, 20.0, 19.9 [00064] L21 (two diastereoisomers) .sup.1H NMR (400 MHz, CDCl.sub.3): 9.21 (s, 1H), 7.43-7.31 (m, 4H), 7.20-7.16 (m, 1H), 7.09 (dd, J = 5.2, 3.7 Hz, 1H), 3.08 (d, J = 14.2 Hz, 1H), 2.78 (d, J = 14.3 Hz, 1H), 2.63-2.52 (m, 2H), 2.10 (s, 3H), 2.06 (s, 3H), 1.61 (s, 3H), 1.53 (s, 3H), 1.29 (t, J = 7.5 Hz, 3H) .sup.13C NMR (101 MHz, CDCl.sub.3): 186.6, 142.1, 140.2, 133.4, 131.4, 130.0, 129.2, 128.0, 127.1, 126.2, 84.2, 52.8, 50.4, 28.8, 28.0, 27.8, 24.9, 19.2, 14.8 .sup.1H NMR (400 MHz, CDCl.sub.3): 9.21 (s, 1H), 7.43-7.36 (m, 2H), 7.33-7.31 (m, 1H), 7.26-7.23 (m, 2H), 7.13-7.10 (m, 1H), 3.06 (d, J = 14.4 Hz, 1H), 2.78 (d, J = 14.2 Hz, 1H), 2.49-2.36 (m, 4H), 2.30-2.19 (m, 1H), 2.12 (s, 3H), 1.65 (s, 3H), 1.63 (s, 3H), 1.07 (t, J = 7.5 Hz, 3H) .sup.13C NMR (101 MHz, CDCl.sub.3): 186.6, 142.4, 139.9, 134.3, 131.4, 130.4, 129.2, 128.0, 127.0, 126.4, 83.9, 52.8, 50.6, 28.8, 28.3, 27.4, 25.0, 19.6, 15.6

##STR00065##

Example III

Synthesis of the Complexes Ru1a-Ru20a by Using CAAC Ligands

Embodiment of the Invention

##STR00066##

[0126] Under an argon atmosphere, the CAACBF.sub.4 ligand (430 mg, 916 mol, 2.20 equiv.), first-generation Hoveyda-Grubbs complex (250 mg, 416 mol, 1.00 equiv.), and anhydrous THF (C.sub.cAc=0.1 M) were placed in a heated Schlenk vessel and stirred for 1 min. LiHMDS (153 mg, 916 mol, 2.20 equiv.) was then added and stirred until full conversion was achieved (20 min). The crude mixture was filtered through neutral alumina (Al.sub.2O.sub.3, neutral, Brockman Grade I) with methylene chloride as eluent. The green fraction was collected and evaporated under reduced pressure. A small amount of n-pentane was then added and the mixture was placed in an ultrasonic bath. The product was filtered off and washed with cold n-pentane. The process was repeated twice and then three times using diethyl ether. After drying under vacuum, a green crystalline solid was obtained in 91% yield (267 mg, 380 mol).

[0127] Using the method presented in Example III, a series of complexes from Ru1a to Ru21a were obtained, the structures of which are shown below.

[0128] All complexes in the table below were characterized by nuclear magnetic resonance spectroscopy. Table 3 summarizes the benzylidene proton shifts of each complex in the .sup.1H NMR spectrum in a given solvent.

TABLE-US-00003 TABLE 3 Summary of the obtained structures of the ruthenium complexes according to Example IV general procedure and the shifts of their benzylidene proton in the .sup.1H NMR spectrum. .sup.1H NMR (ppm) Molar mass Ru = CH Structure/Symbol Molecular formula [g/mol] (solvent) [00067] C.sub.31H.sub.39Cl.sub.2NORuS 645.6890 18.03, 16.84, 16.54 CDCl.sub.3 Ru1a [00068] C.sub.35H.sub.47Cl.sub.2NORuS 701.7970 17.89 CDCl.sub.3 Ru2a [00069] C.sub.33H.sub.43Cl.sub.2NORuS 673.7430 16.38, 16.34 CDCl.sub.3 Ru3a [00070] C.sub.31H.sub.39Cl.sub.2NORuS 645.6890 16.31, 16.30 CD.sub.2Cl.sub.2 Ru4a [00071] C.sub.35H.sub.47Cl.sub.2NORuS 701.7970 17.98, 16.74 CD.sub.2Cl.sub.2 Ru5a [00072] C.sub.33H.sub.44Cl.sub.2NORuS 674.7510 16.39, 16.39, 16.35, 16.34 CDCl.sub.3 Ru6a [00073] C.sub.32H.sub.41Cl.sub.2NORuS 659.7160 16.43, 16.40 CDCl.sub.3 Ru7a [00074] C.sub.36H.sub.49Cl.sub.2NORuS 715.824 16.33, 16.32 CDCl.sub.3 Ru8a [00075] C.sub.34H.sub.46Cl.sub.2NORuS 688.7780 16.47, 16.46, 16.42, 16.41 CDCl.sub.3 Ru9a [00076] C.sub.35H.sub.42Cl.sub.2NORuS 696.7570 16.39, 16.34 CD.sub.2Cl.sub.2 Ru10a [00077] C.sub.39H.sub.49Cl.sub.2NORuS 751.8570 18.16, 16.80 CD.sub.2Cl.sub.2 Ru11a [00078] C.sub.37H.sub.45Cl.sub.2NORuS 723.8030 16.45, 16.43, 16.40, 16.38 CD.sub.2Cl.sub.2 Ru12a [00079] C.sub.35H.sub.41Cl.sub.2NO.sub.2Ru 679.6880 16.18, 16.16 CD.sub.2Cl.sub.2 Ru13a [00080] C.sub.39H.sub.49Cl.sub.2NO.sub.2Ru 735.7960 18.29, 16.52 CD.sub.2Cl.sub.2 Ru14a [00081] C.sub.37H.sub.45Cl.sub.2NO.sub.2Ru 707.7420 16.22, 16.18 CD.sub.2Cl.sub.2 Ru15a [00082] C.sub.36H.sub.43Cl.sub.2FeNORu 733.5610 16.23, 16.21 CD.sub.2Cl.sub.2 Ru16a [00083] C.sub.37H.sub.45Cl.sub.2FeNORu 747.1271 16.36 CDCl.sub.3 Ru17a [00084] C.sub.39H.sub.49Cl.sub.2FeNORu 775.6420 16.46 CDCl.sub.3 Ru18a [00085] C.sub.37H.sub.45Cl.sub.2FeNORu 747.5880 16.26, 16.20 CD.sub.2Cl.sub.2 Ru19a [00086] C.sub.14H.sub.53Cl.sub.2FeNORu 803.6960 18.44, 16.31 CDCl.sub.3 Ru20a [00087] C.sub.30H.sub.37Cl.sub.2NORuS 631.6620 16.29, 16.24 CD.sub.2Cl.sub.2 Ru21a

Example V

Study of the Activity of Complexes in the Ethenolysis Reaction of Methyl Oleate

[0129] Methyl oleate was degassed by stirring for a minimum of 30 minutes under reduced pressure (oil pump). During this time, a closed Schlenk vessel was prepared and weighed to obtain tare. The oil was then filtered through a syringe filter into the Schlenk vessel and the vessel was weighed together with the oil, thus obtaining the weight of the oil. The vessel with the substrate was subjected to reduced pressure. In a separate vessel, a catalyst solution (3 mg in 2 mL of degassed toluene) was prepared. A preheated glass insert for the Amar reactor equipped with a stirring element was placed in the Amar reactor immersed in a preheated oil bath. The reactor was closed and the gas inside was evacuated using an oil pump. A portion of the catalyst (10 ppm or 3 ppm or 500 ppb) was added to the Schlenk vessel containing the oil and the mixture was immediately transferred into the reactor using a Teflon tube. The reactor was filled with ethylene to a dynamic pressure of 10 bar, then stirring was started and the reaction was run for 3 hours or 6 hours. The glovebox and inert gas atmosphere (argon) were not used during the reaction.

[0130] After that time, pressure was normalized and the autoclave was disassembled. SnatchCat metal scavenger (scavenger) solution was immediately added and the contents of the vessel were stirred for several minutes. A sample was then taken and, after dilution with toluene, subjected to GC analysis.

##STR00088##

[0131] The results of the model reaction are shown in Table 2.

TABLE-US-00004 TABLE 4 Comparison of the selectivity of the new ruthenium complexes and ruthenium complexes known from the literature in the process of ethenolysis Ethenolysis results No. Structure Loading [ppm] TON Selectivity 1. [00089] 100 10 5,300.sup.1 35,000.sup.1 73% 83% Literature state-of-the-art 2. [00090] 100 10 5,800.sup.2 26,000.sup.2 96% 97% Literature state-of-the-art 3. [00091] 3 .sup.3 Literature state-of-the-art 4. [00092] 3 47,000.sup.3 63% Literature state-of-the-art 5. [00093] 10 .sup.4 Literature state-of-the-art 6. [00094] 10 19,000.sup.4 92% Literature state-of-the-art 7. [00095] 3 0.5 113,000 101,000 88% 88% Ru2a 8. [00096] 3 0.5 189,000 255,000 88% 88% Ru5a 9. [00097] 3 0.5 48,000 57,000 98% 96% Ru8a 10. [00098] 3 0.5 136,629 182,700 88% 88% Ru11a 11. [00099] 3 0.5 87,612 130,656 88% 81% Ru14a 12. [00100] 10 3 52,713 99,006 92% 94% Ru16a 13. [00101] 10 3 65,363 94,668 92% 95% Ru17a 14. [00102] 10 3 2,507 3,187 99% 100% Ru18a 15. [00103] 10 (isomer ratio = 1:1) 3 (isomer ratio = 1:1) 40,447 69,881 95% 97% Ru19a 16. [00104] 10 3 0.5 20,297 28,953 34,280 49% 54% 39% Ru20a 17. [00105] 10 3 44,000 90,000 94% 96% Ru21a Example 1: ethylene 99.9%, <30 min, 40 C., pressure of 10 bar Example 2: 4 hours, 40 C., pressure of 10 bar Examples 3 and 4: ethylene 99.95%, 3 hours, 40 C., pressure of 10 bar Examples 5 and 6: ethylene, 99.99%, 4 hours, 40 C., pressure of 10 bar Examples 7-17: reactions for 10 ppm: ethylene 99.95%, 3 hours, 40 C.; reactions for 3 ppm: ethylene 99.95%, 3-6 hours, 40 C.; reactions for 0.5 ppm: ethylene 99.995%, 6 hours, 40 C. (ethylene pressure of 10 bar) .sup.1Grubbs et al. Organometallics 2008, 27, 563-566. .sup.2Zhang et al. Chem. Commun., 2013, 49, 9491-9493. .sup.3Bertrandt et al. Angew. Chem. Int. Ed., 2015, 54, 1919-1923. .sup.4Gawin et al. Angew. Chem. Int. Ed. 2017, 56, 981-986.

Example VI

[0132] Testing the activity of the ruthenium complex in the ethenolysis reaction of methyl oleate outside the glovebox under conditions that do not require an inert gas protective atmosphere (FIG. 3). FIG. 3 shows A) the autoclave assembled in air, B) the open autoclave before the ethenolysis reaction.

[0133] The corresponding ethenolysis reactions described in Example V were performed outside the glovebox in an autoclave apparatus placed under the fume hood and located in the airthe reaction system shown in FIG. 3. Subsequent reaction steps were performed in the air without an inert gas protective atmosphere. Ethylene of different purities was used during the reaction, with the purity of ethylene being lower than that described in previous literature reports. Using the new ruthenium complexes Ru1a-Ru22a was observed to be resistant to the use of lower quality ethylene, which did not impair the reaction results as determined by TON and selectivity.

Example VII

Synthesis of a CAAC Ligand and a Spiro Carbon Catalyst

##STR00106##

Synthesis of Compound I

[0134] Aluminium(III) chloride (14.3 g, 105 mmol, 1.00 equiv.) and anhydrous DCM (100 mL) were placed under an argon atmosphere in a three-neck flask equipped with a stirring element, and the suspension was cooled to 40 C. In a two-neck flask under an argon atmosphere equipped with a stirring element, ferrocene (20.0 g, 105 mmol, 1.00 equiv.) was dissolved in anhydrous DCM (155 mL) and added dropwise into the aluminum(III) chloride suspension in DCM at 40 C. with stirring. The mixture was then cooled to 78 C. and acryloyl chloride (9.81 mL, 116 mmol, 1.10 equiv.) was added dropwise for 30 min at 78 C. The reaction was carried out for 18 hours at 78 C., then the contents of the flask were poured into water at 0 C. The organic layer was separated, washed with brine, dried over MgSO.sub.4, the drying agent was filtered through neutral Celite and the solvent was evaporated. The crude product was purified by column chromatography (Al.sub.2O.sub.35% H.sub.2O) to give the product as an orange solid (7.99 g, 33.3 mmol, 31%).

[0135] .sup.1H NMR (400 MHz, CDCl.sub.3): 4.87-4.79 (m, 2H), 4.66-4.56 (m, 2H), 4.43-4.30 (m, 2H), 4.10-3.94 (m, 2H), 3.06-2.86 (m, 4H).

[0136] .sup.13C NMR (101 MHz, CDCl.sub.3): 212.0, 88.2, 74.1, 72.8, 71.2, 70.4, 69.4, 44.3, 31.9.

Synthesis of Compound II

[0137] Ketone I (1.16 g, 4.83 mmol, 1.0 equiv.), Me.sub.3SBr (0.98 g, 6.28 mmol, 1.3 equiv.), KOH (0.70 g, 12.6 mmol, 2.6 equiv.), distilled water (0.25 mL), and MeCN (10 mL) were placed in a reaction vessel equipped with a stirring element under an argon atmosphere. The contents of the vessel were stirred for 16 h at 60 C. After completion of the reaction, 5 mL of diethyl ether (Et.sub.2O) was added, the precipitate was filtered off, and the precipitate was washed again with diethyl ether (10 mL), the solvent was evaporated under reduced pressure. The residue was washed with diethyl ether (10 mL), the solvent evaporated and washed with n-hexane (10 mL), the solvent evaporated under reduced pressure to give the product as an orange solid (1.02 g, 4.01 mmol, 83%).

[0138] .sup.1H NMR (400 MHz, CDCl.sub.3): 4.44-4.35 (m, 1H), 4.25-4.22 (m, 1H), 4.19-4.16 (m, 2H), 4.10-4.04 (m, 4H), 2.95 (d, J=5.5 Hz, 1H), 2.90 (dd, J=0.6, 5.4 Hz, 1H), 2.33-2.16 (m, 3H), 2.09-1.99 (m, 1H).

[0139] .sup.13C NMR (101 MHz, CDCl.sub.3): 86.6, 81.8, 70.9, 69.1, 68.9, 68.8, 68.7, 68.5, 68.4, 67.7, 56.4, 55.0, 42.5, 22.9.

Synthesis of Compound III

[0140] Epoxide II (0.94 g, 3.68 mmol, 1 equiv.), zinc(II) chloride (0.50 g, 3.68 mmol, 1 equiv.) and toluene (16 mL) were placed in a reaction vessel equipped with a stirring element. The reaction was carried out for 2 hours at room temperature. The reaction mixture was filtered off on a Schott funnel, the solvent was distilled off under reduced pressure to give the product as a bright orange solid (0.77 g, 3.04 mmol, 82%).

[0141] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.82 (d, J=1.5 Hz, 1H), 4.22-4.19 (m, 1H), 4.18-4.15 (m, 1H), 4.14-4.11 (m, 3H), 4.10-4.07 (m, 1H), 4.06-4.01 (m, 2H), 2.82-2.74 (m, 1H), 2.54-2.39 (m, 2H), 2.05-1.93 (m, 1H), 1.86-1.72 (m, 1H).

[0142] .sup.13C NMR (101 MHz, CDCl.sub.3): 201.4, 86.4, 81.4, 71.5, 71.4, 70.0, 69.8, 68.9, 68.1, 68.0, 67.3, 50.4, 35.8, 23.9.

Synthesis of Compound IV

[0143] In a round-bottom flaskpreviously heated under reduced pressureunder an argon atmosphere, aldehyde III (0.7 g, 2.76 mmol, 1.0 equiv.), 2-ethyl-6-methylaniline (0.38 g, 2.76 mmol, 1.0 equiv.), 4 molecular sieves (0.7 g), and methylene chloride (5.5 mL) were placed. The reaction was carried out for 16 h at room temperature. The molecular sieves were filtered off, the solvent was evaporated under reduced pressure to give the product as an orange solid. (0.56 g, 1.49 mmol, 54%).

[0144] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 7.75 (d, J=4.7 Hz, 1H), 7.05-6.96 (m, 2H), 6.91 (t, J=7.5 Hz, 1H), 4.22-4.18 (m, 1H), 4.16-4.12 (m, 2H), 4.13-4.05 (m, 4H), 4.06-4.00 (m, 1H), 3.08-2.94 (m, 1H), 2.57-2.47 (m, 2H), 2.43 (q, J=7.5 Hz, 2H), 2.30-2.16 (m, 1H), 2.04 (s, 3H), 2.01-1.90 (m, 1H), 1.08 (t, J=7.5 Hz, 3H).

[0145] .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): 169.2, 151.0, 133.5, 128.2, 127.0, 126.6, 123.7, 86.9, 85.2, 71.6, 71.0, 69.6, 68.5, 68.2, 68.1, 67.2, 43.9, 39.2, 24.9, 24.4, 18.5, 14.9.

Synthesis of Compound V

[0146] Imine IV (0.55 g, 1.47 mmol, 1.00 equiv.) and anhydrous tetrahydrofuran (3.0 mL) were placed in a round-bottom flaskpreviously heated under reduced pressureunder an argon atmosphere. The mixture was then cooled to 78 C. in a dry ice-acetone cooling bath. A solution of n-BuLi (2.30 M solution in n-hexane, 0.77 mL, 1.76 mmol, 1.20 equiv.) was then added dropwise with intense stirring, followed by heating to room temperature. After one hour, the reaction mixture was cooled again to 78 C. in a dry ice-acetone cooling bath and 3-chloro-2-methylpropene (0.22 mL, 2.2 mmol, 1.50 equiv.) was added dropwise. The reaction was carried out for 16 h at room temperature. The solvent was evaporated under reduced pressure. The crude product was filtered through a syringe filter to give the product as a red oil. (0.51 g, 1.19 mmol, 80%).

[0147] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.84 (s, 1H), 7.10-7.03 (m, 1H), 7.06-6.99 (m, 1H), 7.00-6.92 (m, 1H), 4.85-4.80 (m, 1H), 4.80-4.75 (m, 1H), 4.25-4.18 (m, 2H), 4.16-4.11 (m, 3H), 4.11-4.05 (m, 1H), 4.08-4.03 (m, 2H), 2.76 (d, J=14.5 Hz, 1H), 2.70-2.64 (m, 1H), 2.58 (d, J=14.5 Hz, 1H), 2.51 (qd, J=1.6, 7.5 Hz, 2H), 2.43-2.32 (m, 2H), 2.24-2.19 (m, 1H), 2.15 (s, 3H), 1.69 (s, 3H), 1.16 (t, J=7.5 Hz, 3H).

[0148] .sup.13C NMR (101 MHz, CDCl.sub.3): 171.3, 150.4, 142.0, 133.3, 128.2, 127.0, 126.3, 123.7, 115.3, 89.6, 87.4, 68.8, 68.8, 68.5, 68.5, 68.4, 68.4, 67.7, 67.7, 46.2, 42.9, 29.8, 25.1, 24.6, 20.6, 19.1, 14.9.

Synthesis of Compound L22

[0149] The imine from the previous step (0.49 g, 1.15 mmol, 1 equiv.) dissolved in anhydrous PhMe (C=500 mM) was placed in a round-bottom flask under an argon atmosphere. The mixture was cooled to 78 C. in a dry ice-acetone cooling bath. HCl solution (0.7 mL, 4 M solution in dioxane, 2.88 mmol, 2.5 equiv.) was then added dropwise and the reaction was carried out for 16 h at 85 C. with vigorous stirring. The solvent was evaporated under reduced pressure. The crude product was dissolved in methylene chloride (about 5 mL), a saturated aqueous solution of NaBF.sub.4 (0.25 g, 2.30 mmol, 2 equiv.) was added and the ion exchange was carried out for 2 h with vigorous stirring. The mixture was extracted three times with methylene chloride, dried with anhydrous magnesium sulfate and filtered through neutral Celite, after which the solvent was evaporated under reduced pressure. The product was precipitated from the DCM:Et.sub.2O mixture to give the product as a light brown solid (0.27 g, 0.53 mmol, 45%).

Synthesis of Compound Ru22a

[0150] Under an argon atmosphere, the CAACBF.sub.4 ligand L22 (174 mg, 340 mol, 1.20 equiv.), the first-generation Hoveyda-Grubbs complex (170 mg, 283 mol, 1.00 equiv.) and anhydrous THF (C.sub.CAAC=0.1 M) were placed in a preheated Schlenk flask and stirred for 1 min. LiHMDS (56 mg, 340 mol, 1.20 equiv.) was then added and stirred until full conversion was achieved (5 min). After this time, copper(I) chloride (56 mg, 566 mol, 2.00 equiv.) was added. The crude mixture was filtered through neutral alumina (Al.sub.2O.sub.3, neutral, Brockman Grade I) with methylene chloride as eluent. The green fraction was collected and the solvent was evaporated under reduced pressure. A small amount of n-pentane was then added and the mixture was placed in an ultrasonic bath. The product was drained and washed with cold n-pentane. The process was repeated twice and then using diethyl ether. After drying under vacuum, a green crystalline solid was obtained (164 mg, 220 mol, 77%).

TABLE-US-00005 Structure/Number Selected analytical data [00107] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): 9.09 (s, 1H), 7.49-7.40 (m, 1H), 7.35 (d, J = 7.7 Hz, 0.62 1H), 7.27 (d, J = 7.2 Hz, 0.38 1H), 7.25 (d, J = 7.3 Hz, 0.38 1H), 7.20 (d, J = 7.5 Hz, 0.62 1H), 4.57-4.52 (m, 0.62 1H), 4.52-4.48 (m, 0.38 1H), 4.40-4.35 (m, 1H), 4.28-4.24 (m, 3H), 4.23-4.19 (m, 1H), 4.19-4.16 (m, 1H), 4.15-4.11 (m, 1H), 2.80 (d, J = 13.9 Hz, 0.62 1H), 2.79 (d, J = 13.9 Hz, 0.38 1H), 2.70- 2.39 (m, 1H + 2 0.31 2H + 1H + 2H), 2.33 (s, 0.38 3H), 2.31-2.22 (m, 0.19 2H), 2.09-1.99 (m, 0.19 2H), 1.96 (s, 0.62 3H), 1.94-1.88 (m, 1H), 1.58 (s, 0.38 3H), 1.55 (s, 0.62 3H), 1.50 (s, 0.62 3H), 1.48 (s, 0.38 3H), 1.26 (t, J = 7.5 Hz, 0.62 3H), 0.99 (t, J = 7.5 Hz, 0.38 3H); .sup.13C NMR (101 MHz, Methylene chloride-d.sub.2): L22 189.7, 189.7, 140.5, 140.4, 134.3, 133.9, 131.9, 131.8, 131.4, 131.4, 130.2, 130.1, 128.3, 128.0, 86.3, 86.0, 84.6, 84.5, 84.4, 84.1, 72.0, 71.8, 71.8, 71.1, 69.9, 69.8, 69.3, 69.2, 69.1, 68.5, 68.4, 67.7, 67.5, 51.2, 51.1, 46.0, 45.7, 45.0, 44.8, 28.4, 27.6, 26.9, 25.5, 24.6, 19.7, 19.3, 19.2, 18.9, 15.6, 15.0 .sup.1H NMR (ppm) Molar mass Ru = CH Structure/Symbol Molecular formula [g/mol] (solvent) [00108] C.sub.37H.sub.43Cl.sub.2FeNORu 745.1115 16.40, 16.36 CDCl.sub.3 Ru22a