LONG SHELF LIFE STABLE ORGANORUTHENIUM COMPLEXES AS (PRE)CATALYSTS FOR OLEFIN METATHESIS

Abstract

Embodiments in accordance with the present invention encompass an organoruthenium compound of the formula I: (I) wherein X, Y, L.sub.1, L.sub.2, L.sub.3, R.sub.1 and R.sub.2 are as defined herein. Also disclosed herein are the use of organoruthenium compound of the formula I as (pre)catalysts for the olefin metathesis reactions, as well as to the process for carrying out the olefin metathesis reaction.

##STR00001##

Claims

1. A compound of the formula II, including all possible enantiomers, diastereomers, geometric or stereoisomers thereof: ##STR00042## wherein: Z is oxygen; R.sub.3 is hydrogen; R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl and NO.sub.2; ##STR00043## is of the formula (III): ##STR00044## wherein: a and b are integers from 0 to 5; each R.sub.8, R.sub.9, R.sub.10 and R.sub.11 may be the same or different and independently of the other selected from the group consisting of hydrogen, halogen, (C.sub.1-C.sub.16)alkyl, (C.sub.1-C.sub.16)alkoxy, (C.sub.1-C.sub.16)perhaloalkyl, (C.sub.3-C.sub.7)cycloalkyl, (C.sub.2-C.sub.16)alkenyl, (C.sub.6-C.sub.14)aryl, (C.sub.6-C.sub.14)perhaloaryl, (C.sub.3-C.sub.12)heterocyclyl, (C.sub.4-C.sub.20)alkylaryl, OR.sub.18, NO.sub.2, COOH, COOR.sub.18, CONR.sub.18R.sub.19, SO.sub.2NR.sub.18R.sub.19, SO.sub.2R.sub.18, CHO, COR.sub.18, wherein R.sub.18 and R.sub.19 are the same or different and each independently selected from the group consisting of (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)perhaloalkyl, (C.sub.6-C.sub.14)aryl, (C.sub.6-C.sub.14)perhaloaryl; L.sub.3 is an N-heterocyclic carbene ligand of the formula (IVA) or (IVB): ##STR00045## wherein: R.sub.12 and R.sub.17 are the same or different and each independently selected from the group consisting of (C.sub.1-C.sub.12)alkyl, (C.sub.3-C.sub.12)cycloalkyl, (C.sub.2-C.sub.12)alkenyl and (C.sub.6-C.sub.14)aryl unsubstituted or substituted by (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.16)perhaloalkyl, (C.sub.3-C.sub.7)cycloalkyl or (C.sub.4-C.sub.20)alkylaryl; R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are the same or different and each independently selected from the group consisting of hydrogen, (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.14)aryl, optionally substituted with at least one of (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)perhaloalkyl, (C.sub.1-C.sub.6)alkoxy or halogen; or R.sub.13, R.sub.14, R.sub.15, R.sub.16 may optionally join together with the carbon atoms to which they are attached to form a fused (C.sub.4-C.sub.8)carbocyclic ring unsubstituted or substituted by (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.16)perhaloalkyl, (C.sub.3-C.sub.7)cycloalkyl or (C.sub.4-C.sub.20)alkylaryl, or a fused aromatic ring unsubstituted or substituted by (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.16)perhaloalkyl, (C.sub.3-C.sub.7)cycloalkyl or (C.sub.4-C.sub.20)alkylaryl.

2. (canceled)

3. (canceled)

4. The compound according to claim 1, wherein: ##STR00046## selected from the group consisting of: a group of the formula (IIIA): ##STR00047## a group of the formula (IIIB): ##STR00048## a group of the formula (IIIC): ##STR00049## a group of the formula (IIID): ##STR00050## a group of the formula (IIIE): ##STR00051## a group of the formula (IIIF): ##STR00052## and a group of the formula (IIIG): ##STR00053##

5. The compound according to claim 1, wherein: L.sub.3 is selected from the group consisting of: ##STR00054##

6. The compound according to claim 1, which is selected from the group consisting of: ##STR00055## ##STR00056## ##STR00057##

7. A process for carrying out a metathesis reaction of olefins, comprising contacting at least one olefin with the compound of claim 1 as a (pre)catalyst.

8. The process according to claim 7, wherein the metathesis reaction is carried out in an organic solvent.

9. (canceled)

10. The process according to claim 7, wherein the metathesis reaction is carried out without any solvent.

11. The process according to claim 7, wherein the metathesis reaction is carried out in the presence of a chemical activator.

12. (canceled)

13. The process according to claim 11, wherein the activator is hydrogen chloride, chlorotrimethylsilane or p-toluenesulfonic acid.

14. The process according to claim 7, wherein the metathesis reaction is a ring-opening metathetic polymerization of dicyclopentadiene.

15. The process according to claim 14, wherein the (pre)catalyst of the general formula 1 is added in the solid form to dicyclopentadiene.

16. The process according to claim 14, wherein the polymerization reaction is initiated by heating the mixture of dicyclopentadiene and the (pre)catalyst of the general formula 1 to a temperature of 30? C. or higher.

17. (canceled)

18. (canceled)

19. The process according to claim 7, wherein the metathesis reaction is carried out in the presence of an additive promoting formation of cross bonds.

20. (canceled)

Description

EXAMPLE 1

Step 1

[0101] ##STR00026##

[0102] A toluene solution of lithium bis(trimethylsilyl)amide (1 M, 12 mL, 1.1 eq.) was added to a suspension of SIMesHBF.sub.4 (5.1 g, 1.15 eq.) in toluene (82 mL). The resulting mixture was stirred at room temperature for 30 min and then placed in an oil bath heated to a temperature of 80? C. After 10 minutes a compound of formula M10 (10 g, 11.3 mmol, 1 eq.) was added and the mixture was stirred for 10 minutes. Next, (E/Z)-2-(prop-1-en-1-yl)phenol (2.27 g, 1.5 eq.) was added and after additional 30 minutes triphenylphosphine was added (1.48 g, 0.5 eq.). The reaction mixture was stirred at 80? C. for 90 minutes, then cooled down to room temperature and filtered through a short pad of silica gel. The silica gel pad was washed with toluene. The crude product was purified by crystallization and recrystallization from dichloromethane/n-heptane mixture, green solid, 4.2 g, 46% yield.

Step 2

[0103] ##STR00027##

[0104] A toluene solution of potassium tert-pentoxide (1.7 M, 1.74 mL, 1.2 eq.) was added to a solution of imine 1 (0.72 g, 1.2 eq.) in tetrahydrofuran (23 mL) and the resulting mixture was stirred at room temperature for 30 min. After that, LatMetSIMesPPh.sub.3 (2 g, 2.47 mmol, 1 eq.) was added and the reaction was stirred at 41? C. for 45 min. The reaction mixture was filtered through a short pad of celite. The celite pad was washed with THF. The solvents were evaporated to dryness and the crude product was crystallized from a dichloromethane/methanol mixture, black crystals, 0.95 g, 51% yield. The compound was characterized by .sup.1H and .sup.13C NMR:

[0105] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=13.94 (s, 1H), 8.46 (s, 1H), 7.50 (d, 1H), 7.36 (ddd, 1H), 7.33 (dd, 1H), 7.18-7.14 (m, 1H), 7.13 (dd, 1H), 7.05 (ddd, 1H), 6.94 (ddd, 1H), 6.77 (s, 2H), 6.64 (s, 2H), 6.54-6.47 (m, 2H), 6.44 (ddd, 1H), 6.26 (d, 1H), 6.20 (ddd, 1H), 3.87-3.75 (m, 4H), 2.30 (s, 6H), 2.21 (s, 6H), 2.07 (s, 6H), 1.23 (s, 3H).

[0106] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=297.4, 215.4, 178.2, 170.7, 158.2, 152.9, 151.7, 139.6, 138.0, 137.8, 137.5, 136.8, 133.2, 132.9, 130.7, 129.6, 129.4, 129.3, 126.1, 125.5, 124.4, 122.4, 118.6, 118.2, 113.4, 112.2, 52.8, 23.1, 21.4, 18.7, 18.6.

EXAMPLE 2

[0107] ##STR00028##

[0108] A toluene solution of potassium tert-pentoxide (1.7 M, 5.23 mL, 1.2 eq.) was added to a solution of imine 2 (2.41 g, 1.2 eq.) in tetrahydrofuran (68.8 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMetSIMesPPh.sub.3 (6 g, 7.4 mmol, 1 eq.) was added and the reaction was stirred at 41? C. for 1 hour. The reaction mixture was filtered through a short pad of celite. The celite pad was washed with THF. The solvents were evaporated to dryness and the crude product was crystallized from a dichloromethane/methanol mixture, black crystals, 4.76 g, 82% yield. The compound was characterized by .sup.1H and .sup.13C NMR:

[0109] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=13.89 (s, 1H), 7.59 (s, 1H), 7.29 (dd, 1H), 7.22 (ddd, 1H), 7.00-6.90 (m, 4H), 6.81 (s, 2H), 6.77 (dd, 1H), 6.68 (ddd, 1H), 6.52 (s, 2H), 6.37-6.31 (m, 2H), 6.09 (d, 1H), 6.01 (ddd, 1H), 3.77-3.67 (m, 2H), 3.60-3.50 (m, 2H), 2.37 (s, 6H), 2.35 (s, 6H), 2.13 (s, 6H), 0.87 (d, 3H), 0.67 (hept, 1H), 0.26 (d, 3H).

[0110] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=292.0, 207.8, 181.3, 172.7, 161.7, 158.4, 152.1, 138.1, 137.9, 137.8, 137.3, 135.7, 135.6, 133.8, 131.8, 129.5, 129.4, 129.2, 128.5, 125.3, 124.8, 123.7, 122.6, 118.7, 115.8, 111.9, 111.6, 52.8, 41.9, 23.5, 21.3, 19.2, 18.7, 18.4.

EXAMPLE 3

[0111] ##STR00029##

[0112] A toluene solution of potassium tert-pentoxide (1.7 M, 0.44 mL, 1.2 eq.) was added to a solution of imine 3 (0.23 g, 1.2 eq.) in tetrahydrofuran (11.9 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMetSIMesPPh.sub.3 (0.5 g, 0.62 mmol, 1 eq.) was added and the reaction was stirred at 41? C. for 1 hour. The reaction mixture was filtered through a short pad of celite. The celite pad was washed with THF. The solvents were evaporated to dryness and the crude product was crystallized from a dichloromethane/methanol mixture, black crystals, 0.23 g, 45% yield. The compound was characterized by .sup.1H and .sup.13C NMR:

[0113] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=13.86 (s, 1H), 7.59 (s, 1H), 7.28 (dd, 1H), 7.21 (ddd, 1H), 6.98-6.88 (m, 4H), 6.78 (s, 2H), 6.75 (dd, 1H), 6.67 (ddd, 1H), 6.53 (s, 2H), 6.34 (ddd, 1H), 6.31 (dd, 1H), 6.08 (d, 1H), 6.00 (ddd, 1H), 3.75-3.65 (m, 2H), 3.58-3.48 (m, 2H), 2.36 (s, 6H), 2.35 (s, 6H), 2.15 (s, 6H), 1.71-1.63 (m, 1H), 1.62-1.55 (m, 1H), 1.55-1.48 (m, 1H), 1.34-1.23 (m, 1H), 1.22-1.12 (m, 1H), 1.03 (qt, 1H), 0.88 (qd, 1H), 0.77 (qt, 1H), 0.53-0.41 (m, 2H), -0.25 (qd, 1H).

[0114] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=291.7, 208.0, 181.2, 172.7, 161.5, 158.4, 152.1, 138.2, 137.9, 137.7, 137.3, 136.1, 135.5, 133.7, 131.8, 129.4 (2?C), 129.0, 128.8, 125.3, 124.6, 123.7, 122.6, 118.6, 115.8, 111.8, 111.6, 52.9, 49.8, 33.9, 29.5, 27.2, 27.0, 25.7, 21.5, 18.7, 18.4.

EXAMPLE 4

[0115] ##STR00030##

[0116] A toluene solution of potassium tert-pentoxide (1.7 M, 0.44 mL, 1.2 eq.) was added to a solution of imine 4 (0.22 g, 1.2 eq.) in tetrahydrofuran (13.9 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMetSIMesPPh.sub.3 (0.5 g, 0.62 mmol, 1 eq.) was added and the reaction was stirred at 41? C. for 1 hour. The reaction mixture was filtered through a short pad of celite. The celite pad was washed with THF. The solvents were evaporated to dryness and the crude product was crystallized from a dichloromethane/methanol mixture, brown powder, 0.20 g, 40% yield. The compound was characterized by .sup.1H and .sup.13C NMR:

[0117] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=14.11 (s, 1H), 9.52 (s, 1H), 8.07 (d, 1H), 7.67 (d, 1H), 7.59 (d, 1H), 7.50-7.38 (m, 3H), 7.32 (dd, 1H), 7.19 (ddd, 1H), 7.15 (ddd, 1H), 6.94 (ddd, 1H), 6.72-6.61 (m, 5H), 6.58 (dd, 1H), 6.26 (d, 1H), 6.21 (ddd, 1H), 3.87-3.74 (m, 4H), 2.21 (s, 6H), 2.19 (s, 6H), 2.08 (s, 6H), 1.26 (s, 3H).

[0118] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=299.1, 214.9, 178.4, 171.2, 153.0, 152.9, 151.2, 139.5, 137.9, 137.7, 137.3, 136.8, 133.4, 133.0, 132.6, 130.7, 129.5, 129.4, 129.3 (2?C), 127.8, 127.3, 125.7, 125.2, 121.7, 119.4, 118.8, 118.5, 112.2, 111.4, 52.7, 22.8, 21.3, 18.7, 18.6.

EXAMPLE 5

Step 1

[0119] ##STR00031##

[0120] A toluene solution of potassium tert-pentoxide (1.7 M, 139 mL, 1.05 eq.) was added to a suspension of SIPrHBF.sub.4 (113 g, 1.05 eq.) in toluene (2050 mL). The resulting mixture was stirred at room temperature for 30 minutes and then placed in an oil bath heated to a temperature of 85? C. After 20 minutes M10 (200 g, 226 mmol, 1 eq.) was added followed by an addition of toluene (50 mL). The mixture was stirred for 30 minutes. After that, (E/Z)-2-(prop-1-en-1-yl)phenol (45.4 g, 1.5 eq.) in toluene (50 mL) was added followed by an addition of triphenylphosphine (59.2 g, 1 eq.). The reaction mixture was stirred at 85? C. for 90 minutes, then cooled down to room temperature and filtered through a short pad of silica. The silica gel pad was washed with toluene. The solvents were evaporated to dryness and the crude product was crystallized from a dichloromethane/methanol mixture, 38.6 g, 19% yield.

Step 2

[0121] ##STR00032##

[0122] A toluene solution of potassium tert-pentoxide (1.7 M, 22 mL, 1.21 eq.) was added to a solution of imine 1 (9.18 g, 1.22 eq.) in tetrahydrofuran (288 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMetSIPrPPh.sub.3 (27.73 g, 31 mmol, 1 eq.) was added and the reaction was stirred at 61? C. for one hour, then cooled down to room temperature and filtered through a short pad of celite. The celite pad was washed with tetrahydrofuran and dichloromethane. The solvents were evaporated to dryness and the crude product was crystallized from a dichloromethane/n-heptane mixture yielded 1B as a mixture of diastereomers, brown powder, 27.05 g, 104% yield of crude product. The brown powder was dissolved in dichloromethane (500 mL). Then, methanol (150 mL) was added portion-wise over a period of 5 hours to a stirring brown solution. The resulting solution was stirred at room temperature for one hour and filtered through a filter paper. Dichloromethane was slowly evaporated to yield 1B as a single diastereomer, black crystals. The product was recrystallized from a dichloromethane/methanol mixture, black crystals, 20.82 g, 80% yield. The compound was characterized by .sup.1H and .sup.13C NMR:

[0123] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=15.12 (s, 1H), 8.55 (s, 1H), 7.59 (d, 1H), 7.36 (ddd, 1H), 7.15-7.06 (m, 3H), 7.06-6.98 (m, 4H), 6.96 (dd, 1H), 6.94-6.88 (m, 3H), 6.65 (ddd, 1H), 6.36 (d, 1H), 6.29 (ddd, 1H), 6.24 (ddd, 1H), 5.71 (d, 1H), 4.16-4.06 (m, 2H), 3.93-3.82 (m, 2H), 3.60 (hept, 2H), 3.26 (hept, 2H), 1.21 (d, 6H), 1.17 (d, 6H), 1.11 (s, 3H), 1.00 (d, 6H), 0.67 (d, 6H).

[0124] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=294.1, 215.5, 179.6, 171.6, 161.6, 153.7, 152.2, 146.8, 146.7, 141.1, 135.8, 133.0, 132.5, 132.2, 132.1, 130.8, 128.5, 126.2, 125.3, 124.8, 124.6, 124.3, 122.1, 118.9, 117.9, 113.1, 112.3, 56.0, 28.9, 28.7, 26.6, 26.5, 23.5, 23.2, 21.1.

EXAMPLE 6

[0125] A compound of this invention was used to show the shelf life stability of the compounds of this invention when compared with an organoruthenium compound disclosed in the art as shown in the Comparative Example 1 below.

[0126] A compound of Example 5, compound 1B, was used in this study: 1B (14.93 mg, 40 mol ppm) was dissolved in 60 mL of Ultrene 99-6, which was designated as formulation A. The resulting solution was stored under argon at room temperature. The shelf life of formulation A was monitored in a test reaction with a freshly prepared formulation B containing HCl (200 mol ppm) once every two weeks.

[0127] A test procedure:

[0128] A solution of hydrogen chloride (4 M solution in 1,4-dioxane, 1.85 ?L, 200 mol ppm) in 5 mL of Ultrene 99-6 was prepared, and was designated as formulation B. The formulation B as formed was added to 5 mL of freshly prepared formulation A (1.244 mg, 40 mol ppm of 1B). The final, reactive formulation contained 20 mol ppm of 1B and 100 mol ppm of HCl. The results are summarized in Table 1.

TABLE-US-00001 TABLE 1 Time seconds Observations 0 Formulations A and B were mixed 6 Gelation point 13 Smoke time Peak exotherm T.sub.max = 202? C.

[0129] The formulation A was then stored at room temperature for 30 weeks. After which time a freshly prepared formulation B (5 mL of Ultrene 99-6 with hydrogen chloride; 4 M solution in 1,4-dioxane, 1.85 ?L, 200 mol ppm) was added to 5 mL of formulation A (1.244 mg, 40 mol ppm of 1B). The final, reactive formulation contained 20 mol ppm of 1B and 100 mol ppm of HCl. The results are summarized in Table 2.

TABLE-US-00002 TABLE 2 Time (seconds Observations 0 Formulations A and B were mixed 2 Gelation point 6 Smoke time Peak exotherm T.sub.max = 203? C.

[0130] It is evident from the data presented in Tables 1 and 2, the catalytic activity of the compound of this invention, i.e., 1B is not negatively affected even after storing at room temperature for 30 weeks. In fact, the solution of formulation A is even more active after 30 weeks than it was immediately after it was prepared.

COMPARATIVE EXAMPLE 1

[0131] LatMetSIMes3D3 (14.11 mg, 40 mol ppm) was dissolved in 60 mL of Ultrene 99-6 giving formulation A. The resulting solution was stored under argon at room temperature. The shelf life of formulation A was monitored in a test reaction with a freshly prepared formulation B containing HCl (200 mol ppm) once every two weeks.

[0132] A test procedure:

[0133] 5 mL of Ultrene 99-6 with hydrogen chloride (4 M solution in 1,4-dioxane, 1.85 ?L, 200 mol ppm) was prepared and designated as formulation B. Formulation B was added to 5 mL of formulation A (1.176 mg, 40 mol ppm of 1B). The final, reactive formulation contained 20 mol ppm of LatMetSIMes3D3 and 100 mol ppm of HCl. The results are summarized in Table 3.

TABLE-US-00003 TABLE 3 Time [s] Observations 0 Formulations A and B were mixed 9 Gelation point 15 Smoke time Peak exotherm T.sub.max = 212? C.

##STR00033##

[0134] 5 mL of fresh formulation B was prepared as described above. Formulation B was added to formulation A (5 mL, 40 mol ppm of LatMetSIMes3D3) which was stored for 2 weeks. The final, reactive concentration contained 20 mol ppm of LatMetSIMes3D3 and 100 mol ppm of HCl. The reactive formulation was gelled and no peak exotherm was observed which was the result of partial catalyst decomposition.

EXAMPLE 7

[0135] ##STR00034##

[0136] A toluene solution of potassium tert-pentoxide (1.7 M, 4.26 mL, 1.2 eq.) was added to a solution of imine 5 (2.27 g, 1.2 eq.) in 1,4-dioxane (56.0 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMetSIMesPCy.sub.3 (5 g, 6.0 mmol, 1 eq.) was added and the reaction was stirred at 95? C. for 2 hours. The reaction mixture was cooled down to room temperature and filtered through a short pad of celite. The celite pad was washed with 1,4-dioxane and dichloromethane. The solvents were evaporated to dryness and the crude product was crystallized from a dichloromethane/n-heptane mixture yielded 5A as a mixture of diastereomers, brown powder, 4.16 g, 84% yield of crude product. The product was recrystallized from a dichloromethane/methanol mixture yielded pure 5A as a mixture of diastereomers, deep brown or black crystals 3.05 g, 61% yield. The pure mixture of diastereomers was dissolved in dichloromethane (30 mL). Then, methanol (45 mL) was added slowly. The resulting solution was stirred at room temperature overnight. The solvents were evaporated slowly to dryness yielded 5A as a single diastereomer, deep brown or black crystals, 3.01 g, 61% yield. The compound was characterized by .sup.1H and .sup.13C NMR:

[0137] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=14.07 (s, 1H), 8.36 (s, 1H), 7.62 (d, 1H), 7.45-7.41 (m, 1H), 7.40 (d, 1H), 7.19-7.14 (m, 1H), 6.97-6.89 (m, 2H), 6.84 (d, 1H), 6.76-6.71 (m, 2H), 6.69-6.62 (m, 3H), 6.38 (d, 1H), 6.26 (d, 1H), 6.24-6.19 (m, 1H), 3.89-3.67 (m, 4H), 2.79 (hept, 1H), 2.28 (s, 6H), 2.19 (s, 6H), 2.07-1.99 (m, 7H), 1.28-1.22 (m, 6H), 0.49 (d, 3H), 0.30 (d, 3H).

[0138] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=296.1, 214.7, 177.9, 169.5, 157.6, 152.9, 152.8, 139.5, 138.1, 137.7, 137.6, 133.1, 133.1, 132.4, 132.3, 131.9, 130.5, 129.6, 129.4, 128.9, 125.5, 125.1, 124.1, 121.8, 118.6, 118.2, 112.0, 52.6, 45.2, 33.3, 24.6, 24.4, 22.4, 21.4, 20.6, 19.0, 18.7.

EXAMPLE 8

[0139] ##STR00035##

[0140] A toluene solution of potassium tert-pentoxide (1.7 M, 4.26 mL, 1.2 eq.) was added to a solution of imine 6 (2.36 g, 1.2 eq.) in 1,4-dioxane (56.0 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMetSIMesPCy.sub.3 (5 g, 6.0 mmol, 1 eq.) was added and the reaction was stirred at 95? C. for 2 hours. The reaction mixture was cooled down to room temperature and filtered through a short pad of celite. The celite pad was washed with 1,4-dioxane and dichloromethane. The solvents were evaporated to dryness and the crude product was crystallized from a dichloromethane/n-heptane mixture yielded 6A as a mixture of diastereomers, brown powder, 4.74 g, 94% yield of crude product. The brown powder was dissolved in a mixture of dichloromethane (30 mL) and methanol (150 mL). The resulting solution was stirred at room temperature overnight. Dichloromethane was slowly evaporated to yield 6A as a single diastereomer, black crystals, 3.18 g, 63% yield. The compound was characterized by .sup.1H and .sup.13C NMR:

[0141] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=14.14 (s, 1H), 8.41 (s, 1H), 7.39 (ddd, 1H), 7.33 (dd, 1H), 7.22-7.14 (m, 1H), 7.08-6.99 (m, 2H), 6.95 (ddd, 1H), 6.72 (d, 4H), 6.61 (dd, 1H), 6.46 (d, 1H), 6.40 (ddd, 1H), 6.30 (d, 1H), 6.23 (ddd, 1H), 3.88-3.70 (m, 4H), 2.29 (s, 6H), 2.19 (s, 6H), 2.09 (s, 6H), 1.76-1.58 (m, 1H), 1.56-1.44 (m, 2H), 1.38-1.28 (m, 1H), 1.03 (qt, 1H), 0.94 (qt, 1H), 0.79 (qt, 1H), 0.60 (qd, 1H), 0.40-0.31 (m, 1H), 0.26-0.08 (m, 2H).

[0142] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=297.0, 296.9, 214.7, 178.2, 170.5, 158.3, 153.0, 152.0, 139.5, 138.0, 137.6, 136.8, 133.2, 133.0, 132.8, 131.5, 129.5, 129.2, 129.1, 126.1, 125.8, 124.3, 122.2, 118.8, 118.2, 113.2, 112.5, 52.6, 48.5, 36.4, 32.8, 32.2, 26.8, 26.8, 26.5, 21.4, 18.8, 18.7.

EXAMPLE 9

[0143] The structure of complex 1B, as illustrated below, was determined by X-ray crystallographic analysis. Crystals of 1B for this analysis were grown from a dichloromethane/n-heptane solution.

TABLE-US-00004 Bond precision: C ? C = 0.0032 A Wavelength=1.54184 Cell: a = 12.5757 (2) b = 14.3682 (2) c = 23.1131 (3) alpha = 84.759 (1) beta = 84.390 (1) gamma = 81.729 (1) Temperature: 100 K Calculated Reported Volume 4100.39 (10) 4100.39 (10) Space group P ?1 P ?1 Hall group ?P 1 Moiety formula C48 H55 N3 O2 Ru S, C48 H56 N3 02 Ru S N3 02 Ru S C48 H55.50 N3 O2 Ru S Sum formula C96 H111 N6 O4 Ru2 S2 C48 H55.50 N3 O2 Ru S Mr 1679.17 839.58 Dx, g cm?3 1.360 1.360 Z 2 4 Mu (mm?1) 3.897 3.897 F000 1762.0 1762.0 F000 1767.63 h, k, lmax 15, 18, 29 15, 18, 28 Nref 17513 16307 Tmin, Tmax 0.795, 0.947 0.599, 1.000 Tmin' 0.749 Correction method = # Reported T Limits: Tmin = 0.599 Tmax = 1.000 AbsCorr = MULTI-SCAN Data completeness = 0.931 Theta (max) = 77.936 R(reflections) = 0.0332 ( 15104) wR2 (reflections) = 0.0975( 16307) S = 1.086 Npar = 991

EXAMPLE 10

Step 1

[0144] ##STR00036##

[0145] SIMesHBF.sub.4 (7.81 g, 19.8 mmol, 1.1 eq.) was placed under argon in a round bottomed flask. Toluene (160 mL) was added and the resulted suspension was heated up to 80? C. Next, LiHMDS (1 M in toluene, 19.8 mL, 1.1 eq.) was added and the mixture was stirred for 3 minutes before an addition of M10 (15.96 g, 18.0 mmol, 1 eq.). After 15 min full conversion of M10 was observed on TLC plate (AcOEt/c-C.sub.6H.sub.12, 1:9, v/v). The temperature was raised to 110? C. and (E/Z)-2-(prop-1-en-1-yl)-6-isopropylphenol (7.29 g, 36.0 mmol, 2 eq.) was added. The resulted mixture was stirred for 20 min before tricyclohexylphosphine (5.55 g, 19.8 mmol, 1.1 eq.) was added. The stirring was continued for additional 2.5 hours. After that time, the reaction mixture was cooled down to room temperature and was filtered through a short pad of celite. The filtrate was concentrated and the crude product was purified by column chromatography (c-C.sub.6H.sub.12 to c-C.sub.6H.sub.12/AcOEt, 98:2, v/v). Solvents were removed and the crude product was crystalized two times from a dichloromethane/methanol mixture, green solid, 5.26 g, 33% yield. The compound was characterized by .sup.1H, .sup.31P and .sup.13C NMR:

[0146] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=15.72 (d, J=1.3 Hz, 1H), 7.09 (bs, 1H), 7.01 (bs, 1H), 6.67 (bs, 1H), 6.93-6.89 (dd, J=7.0, 1.6 Hz, 1H), 6.27 (dd, J=7.7, 1.7 Hz, 2H), 6.22-6.20 (m, 1H), 3.98 (ddd, J=11.5, 9.0, 7.2 Hz, 1H), 3.81-3.68 (m, 3H), 3.60 (ddd, J=10.4, 9.2, 7.2 Hz, 1H), 2.67 (s, 3H), 2.53 (d, J=9.1 Hz, 6H), 2.35 (s, 3H), 2.28 (s, 3H), 1.67-1.64 (m, 3H), 1.62-1.54 (m, 9H), 1.44-1.41 (m, 3H), 1.19-1.16 (m, 9H), 1.10-1.00 (m, 9H), 0.97-0.94 (m, 3H), 0.84 (qt, J=12.4, 2.8 Hz, 3H), 0.67 (qt, J=12.8, 3.0 Hz, 3H).

[0147] .sup.31P NMR (CD.sub.2Cl.sub.2, 240 MHz): ? [ppm]=28.05.

[0148] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=281.4, 222.5, 222.0, 178.1, 147.9, 139.9, 139.5, 138.9, 137.7, 137.6, 137.5, 137.1, 135.9, 134.7, 130.4, 130.3, 129.9, 129.1, 125.8, 120.5, 111.7, 51.8, 51.7, 32.3, 32.2, 29.4, 29.1, 28.2, 28.2, 28.1, 28.1, 27.1, 25.8, 24.0, 23.8, 21.7, 21.3, 19.6, 19.2, 18.8, 16.9.

Step 2

[0149] ##STR00037##

[0150] A toluene solution of potassium tert-pentoxide (1.7 M, 0.34 mL, 1.2 eq.) was added to a solution of imine 2 (0.157 g, 1.2 eq.) in 1,4-dioxane (5 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMet(6-iPr)SIMesPCy.sub.3 (0.42 g, 0.48 mmol, 1 eq.) was added and the reaction was stirred at 95? C. for 3 hours. The reaction mixture was filtered through a short pad of celite. The celite pad was washed with 1,4-dioxane. The solvents were evaporated to dryness. Crude product was dissolved in dichloromethane (3 mL) and heptane (15 mL). Brownish solid was filtered off and rejected. The filtrate was concentrated to dryness and crude product was crystalized from a dichloromethane/methanol mixture. Dark-brown crystals were filtered off, washed with methanol and dried, 0.19 g, 40% yield. The compound was characterized by .sup.1H and .sup.13C NMR:

[0151] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=13.68 (s, 1H); 7.56 (s, 1H); 7.28-7.25 (m, 1H); 7.21-7.16 (m, 1H); 6.98-6.86 (m, 4H); 6.76-6.69 (m, 3H); 6.55-6.49 (m, 3H); 6.31-6.26 (m, 1H); 6.19-6.14 (m, 1H); 5.96-5.91 (m, 1H); 3.76-3.66 (m, 2H); 3.58-3.48 (m, 2H); 2.82 (sept, 1H, J=7.2 Hz); 2.39 (s, 6H); 2.37 (s, 6H); 2.10 (s, 6H); 1.05 (d, 3H, J=7.2 Hz); 0.86 (d, 3H, J=7.2 Hz); 0.63 (d, 3H, J=7.2 Hz); 0.55 (sept, 1H, J=7.2 Hz); 0.35 (d, 3H, J=7.2 Hz).

[0152] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=289.1, 208.4, 179.2, 172.8, 160.9, 157.4, 151.2, 138.0, 137.7, 137.1, 136.8, 136.7, 135.3, 134.9, 133.0, 131.1, 129.2, 128.7, 128.5, 128.0, 124.4, 124.0, 123.9, 122.7, 121.2, 115.1, 111.0, 110.7, 52.3, 25.9, 24.3, 22.9, 20.8, 20.2, 18.6, 18.3, 17.8.

EXAMPLE 11

[0153] ##STR00038##

[0154] A toluene solution of potassium tert-pentoxide (1.7 M, 0.81 mL, 1.2 eq.) was added to a solution of imine 1 (0.33 g, 1.2 eq.) in 1,4-dioxane (11 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMet(4-NO.sub.2)SIMesPCy.sub.3 (1.0 g, 1.14 mmol, 1 eq.) was added and the reaction was stirred at 95? C. for 1.5 hour. The reaction mixture was cooled down to room temperature and concentrated to 40% of original volume. Crude product was filtered off, washed with toluene and methanol and recrystallized from a dichloromethane/methanol mixture, dark-green crystals, 0.72 g, 79% yield. The product was characterized by .sup.1H and .sup.13C NMR.

[0155] Two diastereomers were observed. The minor diastereomer with the characteristic benzylidene proton signal at 14.57 ppm and the major diastereomer (95%) with the characteristic benzylidene proton signal at 14.02 ppm.

[0156] Peaks of the major diastereomer in .sup.1H and .sup.13C NMR:

[0157] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=14.02 (s, 1H); 8.52 (s, 1H); 7.87-7.81 (m, 1H); 7.50-7.42 (m, 2H); 7.41-7.34 (m, 2H); 7.25-7.17 (m, 2H); 7.14-7.08 (m, 1H); 6.84 (s, 2H); 6.63 (s, 2H); 6.59-6.50 (m, 2H); 6.17 (d, 1H, J=9.0 Hz); 3.90-3.78 (m, 4H); 2.33 (s, 6H); 2.21 (s, 6H); 2.08 (s, 6H); 1.25 (s, 3H).

[0158] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=295.5, 295.4, 211.6, 181.4, 170.6, 158.9, 151.3, 150.3, 138.9, 138.4, 137.9, 137.5, 136.9, 134.9, 133.8, 131.4, 130.6, 129.6, 129.5, 129.5, 127.6, 126.7, 123.9, 122.2, 120.2, 118.2, 117.0, 114.3, 52.5, 24.9, 21.4, 18.4, 18.3.

EXAMPLE 12

Step 1

[0159] ##STR00039##

[0160] Toluene (30 mL) was added to the G2 (3 g, 3.53 mmol, 1 eq.) placed in a round bottomed flask. Next, (E/Z)-2-(prop-1-en-1-yl)-4-methoxyphenol (0.75 g, 4.59 mmol, 1.3 eq.) and tricyclohexylphosphine (1.29 g, 4.59 mmol, 1.3 eq.) were added. The reaction mixture was stirred at 80? C. for 6 hours and then cooled down to room temperature. Half of the toluene was removed on rotavapor and heptane (15 mL) was added. The sticky solid was filtered off on Celite and rejected. The filtrate was evaporated to dryness and a solid residue was further dried on high vacuum. The crude product was crystalized from a dichloromethane/methanol mixture, olive-green solid, 2.6 g, 86% yield. The compound was characterized by .sup.1H and .sup.31P NMR:

[0161] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=15.59 (s, 1H), 7.06 (s, 1H), 6.69 (d, J=8.4 Hz, 2H); 6.83-6.75 (m, 1H); 6.56 (d, J=9.0 Hz, 1H); 6.34 (s, 1H); 5.96 (d, J=3 Hz, 1H); 4.02-3.93 (m, 1H); 3.83-3.69 (m, 2H); 3.67 (s, 3H); 3.65-3.58 (m, 1H); 2.61 (s, 3H); 2.53 (s, 3H); 2.51 (s, 3H); 2.34 (s, 3H); 2.28 (s, 3H); 1.72-1.38 (m, 15H); 1.29 (s, 3H); 1.14-0.97 (m, 9H), 0.97-0.66 (m, 9H).

[0162] .sup.31P NMR (CD.sub.2Cl.sub.2, 240 MHz): ? [ppm]=28.45.

Step 2

[0163] ##STR00040##

[0164] A toluene solution of potassium tert-pentoxide (1.7 M, 0.49 mL, 1.2 eq.) was added to a solution of imine 2 (0.23 g, 1.2 eq.) in 1,4-dioxane (7 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMet(4-OMe)SIMesPCy.sub.3 (0.6 g, 0.7 mmol, 1 eq.) was added and the reaction was stirred at 95? C. for 5 hours. The reaction mixture was filtered through a short pad of celite. The celite pad was washed with 1,4-dioxane. The solvents were evaporated to dryness. Crude product was dissolved in dichloromethane (3 mL) and heptane (15 mL) was added. Brownish solid was filtered off and rejected. The filtrate was concentrated to ca. 10 mL and stored overnight in a fridge. Dark-brown crystals were filtered off and dried, 0.53 g, 93% yield. The compound was characterized by .sup.1H and .sup.13C NMR. Two diastereomers of the product were observed. Only characteristic benzylidene protons and carbene carbons signals are provided:

[0165] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=13.67 (s, 0.93H), 13.60 (s, 1.06H).

[0166] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=292.3, 287.4.

EXAMPLE 13

[0167] ##STR00041##

[0168] A toluene solution of potassium tert-pentoxide (1.7 M, 0.49 mL, 1.2 eq.) was added to a solution of imine 1 (0.20 g, 1.2 eq.) in 1,4-dioxane (7 mL) and the resulting mixture was stirred at room temperature for 30 minutes. After that, LatMet(4-OMe)SIMesPCy.sub.3 (0.6 g, 0.7 mmol, 1 eq.) was added and the reaction was stirred at 95? C. for 3.5 hours. The reaction mixture was filtered through a short pad of celite. The celite pad was washed with 1,4-dioxane. The solvents were evaporated to dryness. Crude product was dissolved in dichloromethane (3 mL) and filtered through Celite again. Heptane (15 ml) was added and dichloromethane was removed on a rotavapor. Crude product was filtered off, washed with heptane and recrystallized from a dichloromethane/methanol mixture, dark-brown crystals, 0.44 g, 80% yield. The compound was characterized by .sup.1H and .sup.13C NMR:

[0169] .sup.1H NMR (CD.sub.2Cl.sub.2, 5.32 ppm; 600 MHz): ? [ppm]=13.63 (s, 1H), 8.45 (s, 1H), 7.49 (d, 1H), 7.38-7.31 (m, 2H), 7.19-7.10 (m, 2H), 7.05 (ddd, 1H), 6.79 (bs, 2H), 6.73 (dd, 1H), 6.65 (bs, 2H), 6.50 (d, 1H), 6.44 (ddd, 1H), 6.20 (d, 1H), 6.00 (d, 1H), 3.87-3.75 (m, 4H), 3.66 (s, 3H), 2.30 (s, 6H), 2.21 (s, 6H), 2.08 (s, 6H), 1.24 (s, 3H).

[0170] .sup.13C NMR (CD.sub.2Cl.sub.2, 54.00 ppm; 150 MHz): ? [ppm]=293.4, 215.4, 174.2, 170.4, 157.9, 151.5, 150.9, 148.5, 139.6, 138.0, 137.7, 137.5, 136.8, 133.1, 132.9, 130.6, 129.4, 129.3, 129.1, 126.0, 124.2, 122.8, 122.3, 118.4, 118.1, 113.3, 106.3, 56.2, 52.6, 22.9, 21.4, 18.6, 18.5.

[0171] Although the invention has been illustrated by certain of the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.