Ruthenium complexes and their use in olefin metathesis reactions

Abstract

The invention relates to a ruthenium complex of formula (1), (1) wherein all variables have a meaning as defined in the specification to be used as a (pre)catalyst in the olefin metathesis reaction, ring metathesis reaction (RCM), homometathesis (self-CM), cross-metathesis including ethanolysis (CM). ##STR00001##

Claims

1. A ruthenium complex of formula 1 ##STR00034## wherein: X.sup.1, X.sup.2 are each independently an anionic ligand selected from such as halogen atom, OR, SR, C(C?O)R, where R is C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.5-C.sub.20 aryl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, optionally C.sub.1-C.sub.12 perhalogenalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom; R.sup.1 is a hydrogen atom or C.sub.5-C.sub.24 aryl, C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.25 heteroaryl, C.sub.7-C.sub.24 aralkyl, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl, optionally C.sub.1-C.sub.12 perhalogenalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom, wherein the alkyl groups may be interconnected to form a ring; R.sup.2 is C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.7-C.sub.24 aralkyl, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl, optionally C.sub.1-C.sub.12 perhalogenalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom, wherein the alkyl groups may be interconnected to form a ring; R.sup.3 is C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 aryl, or C.sub.5-C.sub.20 heteroaryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perhalogenalkyl, C.sub.2-C.sub.12 alkoxy or a halogen atom; R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 are each independently a hydrogen atom, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 aryl, or C.sub.5-C.sub.20 heteroaryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perhalogenalkyl, C.sub.1-C.sub.12 alkoxy or a halogen atom, and the R.sup.4 and R.sup.5 and/or R.sup.8 and R.sup.9 groups may optionally be interconnected to form a cyclic system C.sub.4-C.sub.10; and a, b, c, dare each independently a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.1-C.sub.25 alkoxy, C.sub.5-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.25 heteroaryl, 3-12-membered heterocycle, wherein the alkyl groups may be interconnected to form a ring; also, each of them can be independently an ether (OR), thioether (SR), nitro (NO2), cyano (CN), amide (CONRR), carboxy and ester (COOR), sulfa (SO2R), sulfonamide (SO2NRR), formyl and ketone (COR) group, in which groups R and R are each C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.24 perfluoroaryl.

2. The complex according to claim 1, characterised in that: X.sup.1 and X.sup.2 are halogen atoms; R.sup.3 is aryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perhalogenalkyl, C.sub.2-C.sub.12 alkoxy or a halogen atom; R.sup.4, R.sup.5, R.sup.8, R.sup.9 are each independently a hydrogen atom, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 aryl, or C.sub.5-C.sub.20 heteroaryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perhalogenalkyl, C.sub.1-C.sub.12 alkoxy or a halogen atom, and the R.sup.4 and R.sup.5 and/or the R.sup.8 and R.sup.9, groups may optionally be interconnected to form a cyclic system C.sub.4-C.sub.10; R.sup.6, R.sup.7 are hydrogen atoms; and a, b, c, dare each independently a halogen atom, an ether (OR), thioether (SR), nitro (NO2), cyano (CN), amide (CONRR), carboxy and ester (COOR), sulfa (SO2R), sulfonamide (SO2NRR), formyl and ketone (COR) group, in which groups R and R are each independently C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.24 perfluoroaryl.

3. The complex according to claim 1, characterised in that: X.sup.1 and X.sup.2 are halogen atoms; R.sup.3 is aryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perhalogenalkyl, C.sub.2-C.sub.12 alkoxy or a halogen atom; R.sup.4, R.sup.5, R.sup.8, R.sup.9 are each independently a hydrogen atom, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 aryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl, and R.sup.4 and R.sup.5 and/or the R.sup.8 and R.sup.9, groups may optionally be interconnected to form a cyclic system C.sub.4-C.sub.10; R.sup.6, R.sup.7 are hydrogen atoms; and a, b, c, dare each independently a halogen atom, an ether (OR), nitro (NO2), amide (CONRR), ester (COOR), sulfa (SO2R), sulfonamide (SO2NRR) group, in which groups R and R are each C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.24 aryl.

4. The complex according to claim 1, characterised in that: X.sup.1 and X.sup.2 are chlorine atoms; R.sup.3 is aryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl; R.sup.4, R.sup.5 are each independently C.sub.1-C.sub.12 alkyl, C.sub.5-C.sub.20 aryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl, and the R.sup.4 and R.sup.5 groups may optionally be interconnected to form a cyclic system C.sub.4-C.sub.10; R.sup.6, R.sup.7 are hydrogen atoms; R.sup.8, R.sup.9 are each independently C.sub.1-C.sub.12 alkyl; and a, b, c, dare each independently a halogen atom, an ether (OR) group, in which group R denotes as follows: C.sub.1-C.sub.25 alkyl.

5. The complex according to claim 1, characterised in that: X.sup.1 and X.sup.2 are chlorine atoms; R.sup.3 is aryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl; R.sup.4, R.sup.5 are each independently C.sub.1-C.sub.12 alkyl, C.sub.5-C.sub.20 aryl, and the R.sup.4 and R.sup.5 groups may optionally be interconnected to form a cyclic system C.sub.4-C.sub.10; R.sup.6, R.sup.7 are hydrogen atoms; R.sup.8, R.sup.9 are each independently methyl groups; and a, b, c, dare each a hydrogen atom or a metoxy (OMe) group.

6. The complex according to claim 1 with a structure represented by a structural formula select from formulas 1a-1j: ##STR00035## ##STR00036## ##STR00037##

7. A method comprising: adding the ruthenium complex according to claim 1 as a (pre)catalyst to a solution to produce an olefin metathesis reaction.

8. The method of claim 7, wherein the adding step is accomplished by using the ruthenium complex according to claim 1 as a (pre)catalyst for a ring metathesis reaction (RCM), homometathesis (self-CM), or cross-metathesis, including ethenolysis (CM).

9. The method of claim 7 wherein the adding step is accomplished by using a solution that is an organic solvent such as toluene, benzene, mesitylene, dichloromethane, ethyl acetate, methyl acetate, tertbutyl methyl ether, or cyclopentylmethyl ether.

10. The method of claim 7 wherein the adding step is accomplished by conducting the olefin metathesis reaction at a temperature between O and 150? C.

11. The method of claim 7 wherein the adding step is accomplished by conducting the olefin metathesis reaction at a temperature between 40 and 120? C.

12. The method of claim 7 wherein the adding step accomplished by conducting the olefin metathesis reaction between 1 minute and 24 hours.

13. The method of claim 7 wherein the adding step is accomplished by using the ruthenium complex according to claim 1 in a quantity of no more than 0.1 mol %.

14. The method of claim 13 wherein the using step is accomplish by adding the ruthenium complex according to claim 1 to the reaction mixture as a solid and/or as a solution in an organic solvent.

15. The method of claim 7 wherein the adding step is accomplished by using a solution that is solvent-free.

Description

EXAMPLE I

Reaction for Obtaining the 1a (Pre)Catalyst

(1) ##STR00013##

(2) To UltraCat complex (2.002 g, 2.0 mmol, 1 molar eq.) dry deoxygenated toluene (20 ml) and 3a benzylidene ligand (0.475 g, 2.00 mmol, 1.0 molar eq.) were added under argon. The whole was stirred for 10 minutes at 80? C. The mixture was cooled to room temperature and most of the toluene was evaporated. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess heptane was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold heptane to give a green crystalline solid1a (pre)catalyst (0.875 g, 61%).

(3) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=18.55 (s, 1H), 8.59-8.45 (m, 2H), 7.65-7.22 (m, 10H), 7.20-6.80 (m, 4H), 6.51-6.39 (m, 1H), 4.10-3.50 (m, 1H), 3.50-2.90 (br, 2H), 2.85-1.75 (m, 7H), 1.47 (s, 3H), 1.40-0.95 (m, 10H), 0.95-0.50 (m, 5H).

(4) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=318.0, 267.7, 148.3, 148.2, 147.6, 143.5, 143.3, 138.2, 134.4 (2C), 132.8 (2C), 131.5, 131.4, 130.4 (2C), 129.9, 129.8, 129.2, 128.5 (2C), 128.4 (3C), 128.3, 127.6 (3C), 127.5, 126.9, 79.0, 65.5 (2C), 46.6, 32.4, 31.4, 30.4, 29.6, 27.3, 25.9, 24.4, 23.3, 14.8, 14.5, 14.4.

(5) HRMS: ESI was calculated for C.sub.41H.sub.49N.sub.3ClRu [M-Cl+CH.sub.3CN].sup.+: 720.2661; found: 720.2673.

EXAMPLE II

Reaction for Obtaining the 1b (Pre)Catalyst

(6) ##STR00014##

(7) To UltraCat complex (2.002 g, 2.0 mmol, 1 molar eq.) dry deoxygenated toluene (20 ml) and 3b benzylidene ligand (0.632 g, 2.00 mmol, 1.0 molar eq.) were added under argon. The whole was stirred for 20 minutes at 80? C. The mixture was cooled to room temperature and most of the toluene was evaporated. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess isopropanol was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold isopropanol to give a green crystalline solid1b (pre)catalyst (1.041 g, 66%).

(8) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=([18.56 (s), 18.49 (s)], 1H), 8.53 (dd, J=19.9; 7.8 Hz, 2H), 7.70-6.80 (m, 13H), 6.43 (dd, J=16.5; 7.8 Hz, 1H), 4.50-3.80 (m, 1H), 3.50-0.35 (m, 27H).

(9) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=317.5, 316.5, 267.6, 267.1, 148.2, 147.9, 147.2, 147.1, 143.6, 143.5, 143.3, 138.3, 138.1, 134.9, 134.3 (2C), 134.1, 134.0, 132.8, 132.6, 131.4 (2C), 130.4, 130.3, 130.3, 130.2, 129.8, 129.7, 129.2, 129.1, 128.7, 128.6, 128.4, 128.2 (2C), 128.1, 127.8, 127.7 (2C), 127.6, 127.5 (2C), 127.3, 127.2, 127.0, 126.8, 79.1, 79.0, 65.4, 65.3, 64.7, 60.6, 46.8, 46.4, 31.4 (2C), 30.3, 30.0, 27.4, 27.3, 26.2, 25.8, 25.7, 24.5, 24.3, 14.9, 14.7, 14.5, 14.4.

(10) HRMS: ESI was calculated for C.sub.39H.sub.45N.sub.2BrClRu [M-Cl].sup.+: 757.1498; found: 757.1469.

EXAMPLE III

Reaction for Obtaining the 1c (Pre)Catalyst

(11) ##STR00015##

(12) To UltraCat complex (1.001 g, 1.0 mmol, 1 molar eq.) dry deoxygenated toluene (10 ml) and 3c benzylidene ligand (0.363 g, 1.00 mmol, 1.0 molar eq.) were added under argon. The whole was stirred for 20 minutes at 80? C. The mixture was cooled to room temperature and most of the toluene was evaporated. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess heptane was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold heptane to give a green crystalline solid1c (pre)catalyst (0.570 g, 68%).

(13) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=([18.55 (s), 18.48 (s)], 1H), 8.53 (dd, J=22.7; 7.9 Hz, 2H), 7.92 (d, J=8.3 Hz, 1H), 7.70-6.75 (m, 12H), 6.43 (dd, J=17.7; 7.8 Hz, 1H), 4.80-3.60 (m, 2H), 3.60-1.70 (m, 12H), 1.70-1.10 (m, 10H), 1.10-0.30 (m, 4H).

(14) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=317.6, 316.3, 267.6, 267.0, 148.3, 147.9, 147.0, 143.6, 143.5, 143.4, 143.3, 141.1 (2C), 138.3, 138.1, 136.2, 136.0, 134.3, 133.9, 133.8, 131.4, 131.4, 130.4, 130.4, 130.3, 130.2, 129.8, 129.7, 129.2, 129.1, 128.7, 128.6, 128.4, 128.2, 128.1, 128.0, 127.8, 127.7, 127.6, 127.5 (2C), 127.0, 126.8, 104.6 (2C), 79.1, 79.0, 65.3, 60.7, 46.8, 46.4, 32.4, 31.4, 30.2, 29.6, 27.4, 27.3, 26.2, 25.7, 24.5, 24.3, 23.2, 14.9, 14.6, 14.5, 14.4 (2C).

(15) HRMS: ESI was calculated for C.sub.39H.sub.45N.sub.2IClRu [M-Cl].sup.+: 805.1359; found: 805.1348.

EXAMPLE IV

Reaction for Obtaining the 1d (Pre)Catalyst

(16) ##STR00016##

(17) To UltraCat complex (1.001 g, 1.0 mmol, 1 molar eq.) dry deoxygenated toluene (10 ml) and 3d benzylidene ligand (0.325 g, 1.00 mmol, 1.0 molar eq.) were added under argon. The whole was stirred for 20 minutes at 80? C. The mixture was cooled to room temperature and most of the toluene was evaporated. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess heptane was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold heptane to give a green crystalline solid1d (pre)catalyst (0.490 g, 61%).

(18) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=[19.62 (s), 18.33 (s), 1H], 8.80-5.80 (m, 18H), 4.50-0.20 (m, 27H).

(19) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=317.6, 311.4, 269.6, 267.1, 150.7, 148.3, 146.5, 143.4, 139.8, 138.2, 137.0, 135.1, 134.2, 132.6, 131.3, 130.9, 129.9, 129.6, 129.2, 128.5, 127.7, 127.5, 127.4, 127.0, 79.2, 66.2, 65.2, 58.8, 57.8, 48.0, 32.4, 31.3, 29.6, 27.7, 26.0, 24.5, 23.3, 14.5.

(20) HRMS: ESI was calculated for C.sub.41H.sub.46N.sub.2ClRuS.sub.2 [M-Cl].sup.+: 767.1834; found: 767.1821.

EXAMPLE V

Reaction for Obtaining the 1e (Pre)Catalyst

(21) ##STR00017##

(22) To UltraCat complex (1.001 g, 1.0 mmol, 1 molar eq.) dry deoxygenated toluene (10 ml) and 3e benzylidene ligand (0.319 g, 1.00 mmol, 1.0 molar eq.) were added under argon. The whole was stirred for 20 minutes at 80? C. The mixture was cooled to room temperature and most of the toluene was evaporated. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess isopropanol was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold isopropanol to give a green crystalline solid1e (pre)catalyst (0.322 g, 40%).

(23) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=[18.25 (s), 18.21 (s), 1H], 8.75-5.80 (m, 20H), 4.50-0.20 (m, 27H).

(24) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=317.3, 267.6, 148.7, 147.8, 146.9, 146.4, 146.3, 143.4, 143.3, 138.2, 135.8, 132.8 (2C), 131.2 (2C), 130.4, 130.0, 129.9 (2C), 129.5, 129.4 (2C), 129.2, 129.1, 129.0, 128.7 (3C), 128.1 (2C), 127.9, 127.7 (2C), 127.5, 127.4, 127.2, 127.1 (2C), 127.0, 126.9 (2C), 126.5, 120.7, 120.5, 115.1, 114.1, 79.2, 77.9, 70.8, 65.1, 63.3, 58.2, 57.6, 47.5, 32.4, 31.5, 29.6, 29.4, 27.5, 26.3, 25.0, 24.4, 23.26, 14.5.

(25) HRMS: ESI was calculated for C.sub.43H.sub.48N.sub.2ClRuS [M-Cl].sup.+: 761.2270; found: 761.2253.

EXAMPLE VI

Reaction for Obtaining the 1f (Pre)Catalyst

(26) ##STR00018##

(27) To UltraCat complex (1.502 g, 1.50 mmol, 1 molar eq.) dry deoxygenated toluene (15 ml) and 3f benzylidene ligand (0.564 g, 1.80 mmol, 1.2 molar eq.) were added under argon. The whole was stirred for 10 minutes at 80? C. The mixture was cooled to room temperature and most of the toluene was evaporated. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess heptane was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold heptane to give a green crystalline solid1f (pre)catalyst (0.931 g, 78%).

(28) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=18.07 (s, 1H), 8.52 (br. s, 2H), 7.90-6.20 (m, 19H), 5.91 (d, J=7.7 Hz, 1H), 4.60-0.20 (m, 27H).

(29) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=320.3, 317.4, 269.4, 267.4, 149.0, 146.4, 143.3, 140.1, 136.5, 132.8, 129.9, 129.7, 129.2, 129.1, 128.7, 128.3, 127.7, 127.4 127.0, 126.5, 79.2, 65.0, 64.7, 58.8, 57.6, 47.2, 31.5, 30.2, 29.2, 27.4, 26.6, 25.7, 24.6, 24.1, 18.3, 14.4.

(30) HRMS: ESI was calculated for C.sub.45H.sub.50N.sub.2ClRu [M-Cl].sup.+: 755.2706; found: 755.2707.

EXAMPLE VII

Reaction for Obtaining the 1g (Pre)Catalyst

(31) ##STR00019##

(32) To UltraCat complex (1.001 g, 1.0 mmol, 1 molar eq.) dry deoxygenated toluene (10 ml) and 3g benzylidene ligand (0.707 g, 1.50 mmol, 1.5 molar eq.) were added under argon. The whole was stirred for 20 minutes at 80? C. The mixture was cooled to room temperature and most of the toluene was evaporated. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess heptane was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold heptane to give a green crystalline solid1g (pre)catalyst (0.425 g, 45%).

(33) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=18.00 (s, 1H), 8.70-8.30 (m, 2H), 7.80-7.05 (m, 13H), 6.90-6.20 (m, 5H), 6.05-5.40 (m, 2H), 5.20-0.20 (m, 25H).

(34) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=319.8, 317.0, 268.6, 266.7, 149.1, 148.6, 146.0, 143.4, 143.0, 138.1, 136.2, 134.6, 132.2, 132.0, 131.9, 131.8, 131.5, 130.4, 130.4, 130.2, 129.9, 129.6, 129.4, 129.2, 128.9, 128.3, 127.8, 127.4, 127.0, 126.5, 123.0, 122.0, 79.3, 65.0, 64.8, 64.6, 64.4, 59.2, 58.7, 58.6, 56.6, 56.2, 47.4, 47.0, 32.4, 31.8, 31.3, 30.4, 29.6, 29.1, 28.9, 28.4, 27.6, 27.4, 27.2, 26.6, 25.4, 24.7, 24.0, 23.9, 23.3, 15.2, 14.8, 14.5, 14.2.

(35) HRMS: ESI was calculated for C.sub.45H.sub.49Br.sub.2N.sub.2Ru [M-2Cl+H].sup.+: 877.1305; found: 877.1319.

EXAMPLE VIII

Reaction for Obtaining the 1h (Pre)Catalyst

(36) ##STR00020##

(37) To UltraCat complex (2.002 g, 2.00 mmol, 1 molar eq.) dry deoxygenated toluene (20 ml) and 3h benzylidene ligand (0.896 g, 2.40 mmol, 1.2 molar eq.) were added under argon. The whole was stirred for 20 minutes at 80? C. The mixture was cooled to room temperature and most of the toluene was evaporated. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess heptane was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold heptane to give a green crystalline solid1h (pre)catalyst (0.450 g, 26%).

(38) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=17.76 (s, 1H), 8.70-8.30 (m, 2H), 7.70-7.00 (m, 14H), 6.95-6.15 (m, 4H), 4.50-0.40 (m, 33H).

(39) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=316.9, 313.9, 270.3, 268.4, 149.8, 149.0, 148.7, 146.8, 143.9, 140.1, 132.8, 130.6, 130.0, 129.3, 128.7, 128.6, 128.0, 127.6, 127.4, 127.3, 127.2, 114.1, 113.3, 112.9, 111.8, 111.0, 110.3, 79.0, 65.1, 58.5, 56.4, 56.2, 47.3, 46.8, 32.4, 31.7, 31.3, 30.6, 29.6, 29.4, 27.6, 27.2, 26.6, 25.5, 24.8, 24.0, 23.2, 15.2, 14.4.

(40) HRMS: ESI was calculated for C.sub.49H.sub.57N.sub.3ClO.sub.2Ru [M-Cl+CH.sub.3CN].sup.+: 856.3188; found: 856.3181.

EXAMPLE IX

Reaction for Obtaining the 1i (Pre)Catalyst

(41) ##STR00021##

(42) To Bis-Me complex (1.316 g, 1.50 mmol, 1 molar eq.) dry deoxygenated toluene (15 ml), 3f benzylidene ligand (0.564 g, 1.80 mmol, 1.2 molar eq.) and CuCl (0.163 g, 1.65 mmol, 1.1 molar eq.) were added under argon. The whole was stirred for 10 minutes at 70? C. The mixture was cooled to room temperature and evaporated to dryness. The residue was dissolved in ethyl acetate and filtered through a pad of Celite and evaporated to dryness. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess heptane was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold heptane to give a green crystalline solid1i (pre)catalyst (0.620 g, 57%).

(43) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=18.36 (s, 1H), 7.55 (t, J=7.7 Hz, 1H), 7.46-7.30 (m, 4H), 7.29-7.02 (m, 9H), 6.95 (td, J=7.5; 1.2 Hz, 1H), 6.85 (dd, J=7.5; 1.3 Hz, 1H), 6.24 (dd, J=7.8; 1.4 Hz, 1H), 4.30-3.70 (m, 4H), 2.90-2.20 (m, 4H), 2.20-1.80 (m, 8H), 1.34-1.16 (m, 8H), 1.10-0.50 (m, 6H).

(44) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=315.6, 315.4, 315.2, 269.9, 148.9, 143.3, 138.4, 135.4, 134.9, 132.7, 130.9, 129.3, 129.0, 128.3, 128.2, 127.6, 127.3, 127.1, 79.8, 59.7, 56.9, 52.7, 31.0, 29.0, 25.1, 14.7.

(45) HRMS: ESI was calculated for C.sub.40H.sub.49N.sub.2Cl.sub.2Ru [M+H].sup.+: 729.2316; found: 729.2307.

EXAMPLE X

Reaction for Obtaining the 1j (Pre)Catalyst

(46) ##STR00022##

(47) To Bis-Cy complex (1.100 g, 1.15 mmol, 1 molar eq.) dry deoxygenated toluene (15 ml), 3f benzylidene ligand (0.396 g, 1.26 mmol, 1.1 molar eq.) and CuCl (0.171 g, 1.72 mmol, 1.5 molar eq.) were added under argon. The whole was stirred for 10 minutes at 70? C. The mixture was cooled to room temperature and evaporated to dryness. The residue was dissolved in ethyl acetate and filtered through a pad of Celite and evaporated to dryness. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess heptane was added. The methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered off and washed with cold heptane to give a green crystalline solid1j (pre)catalyst (0.585 g, 66%).

(48) .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): ?=18.48 (s, 1H), 8.00-6.40 (m, 16H), 6.28-6.23 (m, 1H), 4.60-1.70 (br m, 17H), 1.56-1.40 (m, 4H), 1.38-1.10 (m, 10H), 0.89 (t, J=7.2 Hz, 3H).

(49) .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): ?=316.0, 269.7, 149.0, 143.3, 138.3, 135.3, 134.9, 132.6, 131.0, 129.4, 129.0, 128.2, 127.7, 127.4, 127.1, 79.7, 63.0, 60.0, 45.0, 36.6, 34.7, 29.4, 26.0, 25.2, 23.6, 22.9, 14.7, 14.4.

(50) HRMS: ESI was calculated for C.sub.43H.sub.52N.sub.2ClRu [M-Cl].sup.+: 733.2863; found: 733.2850.

EXAMPLE XI

Obtaining the 3a Ligand

(51) ##STR00023##

(52) To a solution of 1,2,3,4-tetrahydroisoquinoline (26.600 g, 200.0 mmol, 2 molar eq.) and triethylamine (10.120 g, 100.0 mmol, 1 molar eq.) in methylene chloride (500 ml) cooled to the temperature of 0? C., benzyl bromide (17.100 g, 100.0 mmol, 1 molar eq.) was added dropwise over 10 minutes. The mixture was slowly heated to room temperature and stirred overnight, then washed with water and dried over Na.sub.2SO.sub.4. The mixture was then filtered, concentrated and distilled under reduced pressure. The product was collected in a fraction with the boiling point of 126-132? C. at a pressure of 1.1?10.sup.?2 mbar (colourless oil, 18.470 g, 83%).

(53) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.49-7.45 (m, 2H), 7.43-7.38 (m, 2H), 7.36-7.32 (m, 1H), 7.21-7.14 (m, 3H), 7.06-7.03 (m, 1H), 3.76 (s, 2H), 3.71 (s, 2H), 2.97 (t, J=5.9 Hz, 2H), 2.82 (t, J=5.9 Hz, 2H).

(54) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=138.4, 134.9, 134.3, 129.0, 128.6, 128.2, 127.0, 126.5, 126.0, 125.5, 62.7, 56.1, 50.6, 29.3.

(55) HRMS: ESI was calculated for C.sub.43H.sub.52N.sub.2ClRu [M-Cl].sup.+: 224.1434; found: 224.1441.

(56) To the amine obtained in the preceding step (12.946 g, 58.0 mmol, 1 molar eq.) in ethanol (96%, 150 ml), methyl iodide (16.460 g, 116.0 mmol, 2 molar eq.) was added. The whole was stirred at the temperature of 35? C. overnight, and the excess of methyl iodide was evaporated under reduced pressure. NaOH (3.480 g, 87.0 mmol, 1.5 molar eq.) was then added. The mixture was heated while boiling with vigorous stirring under reflux overnight, then cooled and evaporated to dryness. The residue was dissolved in methylene chloride, washed with water and dried over Na.sub.2SO.sub.4, then filtered and evaporated to dryness. The crude product was filtered through a thin layer of silica gel (eluent: ethyl acetate/cyclohexane 5:95) and then concentrated to dryness to obtain a colourless oilthe 3a ligand (12.711 g, 92%).

(57) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.53 (dd, J=7.5; 1.6 Hz, 1H), 7.35-7.27 (m, 5H), 7.26-7.19 (m, 3H), 7.17 (dd, J=17.5; 10.9 Hz, 1H), 5.65 (dd, J=17.6; 1.5 Hz, 1H), 5.26 (dd, J=11.0; 1.5 Hz, 1H), 3.55 (s, 2H), 3.51 (s, 2H), 2.14 (s, 3H).

(58) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=139.4, 137.7, 136.2, 134.9, 130.4, 129.0, 128.1, 127.3, 126.9, 125.6, 114.8, 62.1, 60.0, 42.0.

(59) HRMS: ESI was calculated for C.sub.17H.sub.20N [M+H].sup.+: 238.1590; found: 238.1596.

EXAMPLE XII

Obtaining the 3b Ligand

(60) ##STR00024##

(61) Molecular sieves (3 ?, 3.6 g) were added to a solution of 1,2,3,4-tetrahydroisoquinoline (3.600 g, 27.0 mmol, 1 molar eq.) and 2-bromobenzaldehyde (5.000 g, 27.0 mmol, 1 molar eq.) in methanol (70 ml). The mixture was heated under reflux for 4 hours. After cooling, the mixture was filtered and the solution was placed in a flask fitted with a reflux condenser. Then, NaBH.sub.4 (2.045 g, 54.0 mmol, 2 molar eq.) was added portionwise to the mixture with vigorous stirring and left overnight at room temperature. 100 ml of water was added to the mixture, methanol was evaporated and extraction was performed using methylene chloride (3?50 ml). The combined organic extracts were washed with water, dried over Na.sub.2SO.sub.4 and evaporated to dryness. The crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane.fwdarw.5:95). The fraction containing the product was evaporated to dryness to obtain a slightly yellow oil (3.673 g, 45%).

(62) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.62-7.55 (m, 2H), 7.31 (td, J=7.4; 1.2 Hz, 1H), 7.18-7.09 (m, 4H), 7.05-6.98 (m, 1H), 3.81 (s, 2H), 3.74 (s, 2H), 2.95 (t, J=5.9 Hz, 2H), 2.84 (t, J=5.9 Hz, 2H).

(63) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=137.7, 134.8, 134.3, 132.7, 130.6, 128.7, 128.9, 127.3, 126.6, 126.1, 125.6, 124.5, 61.5, 56.0, 50.8, 29.2.

(64) HRMS: ESI was calculated for C.sub.16H.sub.17BrN [M+H].sup.+: 302.0539; found: 302.0545.

(65) To the solution of the amine obtained in the preceding step (3.673 g, 12.15 mmol, 1 molar eq.) in methylene chloride (35 ml), methyl iodide (3.45 g, 24.31 mmol, 2 molar eq.) was added. The whole was stirred at the temperature of 35? C. overnight, evaporated to dryness, after which ethanol (96%, 35 ml) and NaOH (0.729 g, 18.23 mmol, 1.5 molar eq.) were added. The mixture was heated under reflux with vigorous stirring overnight. The mixture was cooled and evaporated to dryness. The residue was dissolved in methylene chloride, washed with water and dried over Na.sub.2SO.sub.4, then filtered and concentrated to dryness. The crude product was filtered through a thin layer of silica gel (eluent: ethyl acetate/cyclohexane 5:95) and then evaporated to dryness to obtain a slightly yellow oilthe 3b ligand (3.459 g, 90%).

(66) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.52 (dd, J=7.9; 1.3 Hz, 2H), 7.48 (dd, J=7.7; 1.7 Hz, 1H), 7.33 (dd, J=7.3; 1.8 Hz, 1H), 7.28-7.20 (m, 3H), 7.17 (dd, J=17.5; 11.0 Hz, 1H), 7.09 (td, J=7.7; 1.8 Hz, 1H), 5.63 (dd, J=17.5; 1.5 Hz, 1H), 5.25 (dd, J=11.0; 1.5 Hz, 1H), 4.09 (d, J=5.8 Hz, 4H), 2.18 (s, 3H).

(67) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=138.4, 137.7, 136.0, 134.9, 132.6, 131.0, 130.4, 128.3, 127.4, 127.4, 127.2, 125.6, 124.6, 114.9, 61.1, 60.1, 42.0.

(68) HRMS: ESI was calculated for C.sub.17H.sub.19BrN [M+H].sup.+: 316.0695; found: 316.0704.

EXAMPLE XIII

Obtaining the 3c Ligand

(69) ##STR00025##

(70) Molecular sieves (3 ?, 1.6 g) were added to a solution of 1,2,3,4-tetrahydroisoquinoline (1.320 g, 9.91 mmol, 1 molar eq.) and 2-iodobenzaldehyde (2.300 g, 9.91 mmol, 1 molar eq.) in methanol (25 ml). The mixture was heated under reflux for 4 hours, and then filtered after cooling. The solution was placed in a flask fitted with a reflux condenser and NaBH.sub.4 (0.750 g, 19.83 mmol, 2 molar eq.) was added portionwise with vigorous stirring. The mixture was left overnight at room temperature, then 50 ml of water was added, methanol was evaporated and extraction was performed using methylene chloride (3?20 ml). The combined organic extracts were washed with water and dried over Na.sub.2SO.sub.4. This was evaporated to dryness, and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The fraction containing the product was evaporated to dryness to obtain a slightly yellow oil (1.18 g, 34%).

(71) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.86 (dd, J=7.9; 1.2 Hz, 1H), 7.53 (d, J=7.7 Hz, 1H), 7.33 (td, J=7.5; 1.2 Hz, 1H), 7.17-7.09 (m, 3H), 7.03-7.00 (m, 1H), 6.97 (td, J=7.7; 1.8 Hz, 1H), 3.73 (s, 4H), 2.94 (t, J=5.9 Hz, 2H), 2.84 (t, J=5.8 Hz, 2H).

(72) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=139.4, 134.3, 130.2, 128.7, 128.7, 128.1, 126.5, 126.1, 125.6, 100.5, 66.3, 55.9, 50.7, 29.2.

(73) HRMS: ESI was calculated for C.sub.16H.sub.17IN [M+H].sup.+: 350.0400; found: 350.0405.

(74) To the solution of the amine obtained in the preceding step (1.181 g, 33.38 mmol, 1 molar eq.) in methylene chloride (10 ml), methyl iodide (0.960 g, 6.76 mmol, 2 molar eq.) was added. The whole was stirred at the temperature of 35? C. overnight, and evaporated to dryness. Ethanol (96%, 10 ml) and NaOH (0.203 g, 5.07 mmol, 1.5 molar eq.) were then added. The mixture was heated while boiling with vigorous stirring under reflux overnight, then cooled and evaporated to dryness. The residue was dissolved in methylene chloride, washed with water and dried over Na.sub.2SO.sub.4, then filtered and evaporated to dryness. The crude product was filtered through a thin layer of silica gel (eluent: ethyl acetate/cyclohexane 5:95) and then concentrated to dryness to obtain a slightly yellow oilthe 3c ligand (1.072 g, 87%).

(75) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.82 (dd, J=7.9; 1.3 Hz, 1H), 7.51 (dd, J=7.3; 1.7 Hz, 1H), 7.44 (dd, J=7.7; 1.7 Hz, 1H), 7.34 (dd, J=7.1; 1.8 Hz, 1H), 7.30 (td, J=7.4; 1.2 Hz, 1H), 7.25-7.20 (m, 2H), 7.15 (dd, J=17.4; 10.9 Hz, 1H), 6.93 (td, J=7.6; 1.7 Hz, 1H), 5.63 (dd, J=17.5; 1.5 Hz, 1H), 5.24 (dd, J=11.0; 1.5 Hz, 1H), 3.62 (s, 2H), 3.58 (s, 2H), 2.17 (s, 3H).

(76) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=141.3, 139.3, 137.7, 136.0, 134.9, 130.6, 130.6, 130.4, 128.6, 128.0, 127.4, 127.3, 125.6, 114.9, 100.6, 66.0 (2C), 59.9 (2C), 42.0.

(77) HRMS: ESI was calculated for C.sub.17H.sub.19IN [M+H].sup.+: 364.0557; found: 364.0574.

EXAMPLE XIV

Obtaining the 3d Ligand

(78) ##STR00026##

(79) To a solution of 1,2,3,4-tetrahydroisoquinoline (7.990 g, 60.0 mmol, 1 molar eq.) in ethanol (96%, 300 ml), K.sub.2CO.sub.3 (20.73 g, 150.0 mmol, 2.5 molar eq.) was added. The mixture was heated while boiling with vigorous stirring using a reflux condenser, 2-(bromomethyl)thiophene (22.310 g, 126.0 mmol, 2.1 molar eq.) was added dropwise over 6 hours. The mixture was heated while boiling over another 6 hours, and then cooled and filtered. NaOH (24.380 g, 150.0 mmol, 2.5 molar eq.) was then added. The mixture was heated under reflux with vigorous stirring over 2 hours. The mixture was then cooled and ethanol was evaporated to obtain yellow oil, which was dissolved in methylene chloride and washed with water. The product was then dried over Na.sub.2SO.sub.4, filtered and concentrated to dryness to obtain a slightly yellow oil. The crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.5:95). The fraction containing the product was evaporated to dryness to obtain a slightly yellow oil (8.600 g, 44%).

(80) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.53-7.47 (m, 2H), 7.26-7.20 (m, 4H), 7.14 (dd, J=17.4; 10.9 Hz, 1H), 6.95-6.91 (m, 4H), 5.61 (dd, J=17.4; 1.5 Hz, 1H), 5.27 (dd, J=11.0; 1.5 Hz, 1H), 3.80 (s, 4H), 3.71 (s, 2H).

(81) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=142.3, 137.7, 135.8, 134.9, 129.8, 127.5, 127.3, 126.4, 126.0, 125.8, 124.9, 115.2, 55.3, 51.6.

(82) HRMS: ESI was calculated for C.sub.19H.sub.20NS.sub.2 [M+H].sup.+: 326.1032; found: 326.1040.

EXAMPLE XV

Obtaining the 3e Ligand

(83) ##STR00027##

(84) Molecular sieves (3 ?, 11.5 g) were added to a solution of 1,2,3,4-tetrahydroisoquinoline (11.88 g, 89.0 mmol, 1 molar eq.) and thiophen-2-carboxyaldehyde (10.0 g, 89.0 mmol, 1 molar eq.) in methanol (100 ml). The mixture was heated under reflux for 4 hours, and then filtered after cooling. The solution was placed in a flask fitted with a reflux condenser. NaBH.sub.4 (3.37 g, 89.0 mmol, 1 molar eq.) was then added portionwise with vigorous stirring and left overnight at room temperature. 200 ml of water was added to the mixture, methanol was evaporated and extraction was performed using methylene chloride (3?100 ml). The combined organic extracts were washed with water, dried over Na.sub.2SO.sub.4 and evaporated to dryness. The crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.1:9). The fraction containing the product was evaporated to dryness to obtain a slightly yellow oil (9.174 g, 45%).

(85) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.24 (dd, J=4.7; 1.6 Hz, 1H), 7.14-7.07 (m, 3H), 7.00-6.93 (m, 3H), 3.89 (d, J=0.8 Hz, 2H), 3.69 (s, 2H), 2.90 (t, J=5.9 Hz, 2H), 2.78 (t, J=5.9 Hz, 2H).

(86) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=141.8, 134.6, 134.3, 128.6, 126.6, 126.4, 126.1, 125.9, 125.6, 125.0, 56.8, 55.7, 50.2, 29.1.

(87) HRMS: ESI was calculated for C.sub.14H.sub.16NS [M+H].sup.+: 230.0998; found: 230.1006.

(88) To the solution the amine obtained in the preceding step (4.326 g, 18.9 mmol, 1 molar eq.) in ethanol (96%, 45 ml), benzyl bromide (3.870 g, 22.6 mmol, 1.2 molar eq.) was added. The mixture was heated while boiling with vigorous stirring under reflux overnight, then cooled and evaporated to dryness, and NaOH (1.13 g, 28.3 mmol, 1.5 molar eq.) was added. The mixture was heated while boiling with vigorous stirring under reflux over 3 hours, then cooled and evaporated to dryness. The residue was dissolved in methylene chloride, washed with water, dried over Na.sub.2SO.sub.4, filtered and evaporated to dryness. The crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 2:98.fwdarw.5:95). The fraction containing the product was evaporated to dryness to obtain a slightly yellow oil (4.986 g, 83%).

(89) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.50-7.44 (m, 2H), 7.41-7.37 (m, 2H), 7.34-7.28 (m, 2H), 7.24-7.19 (m, 4H), 7.07 (dd, J=17.4; 10.9 Hz, 1H), 6.94-6.91 (m, 1H), 6.90-6.88 (m, 1H), 5.59 (dd, J=17.4; 1.6 Hz, 1H), 5.23 (dd, J=10.9; 1.5 Hz, 1H), 3.74 (s, 2H), 3.64 (s, 2H), 3.57 (s, 2H).

(90) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=142.6, 139.1, 137.7, 136.1, 135.0, 130.0, 128.9, 128.3, 128.2, 127.7, 127.5, 127.4, 127.2, 127.0, 126.3, 125.9, 125.7, 124.8, 114.9, 72.7, 65.7, 57.6, 31.0, 29.0, 55.7, 52.1.

(91) HRMS: ESI was calculated for C.sub.21H.sub.22NS [M+H].sup.+: 320.1467; found: 320.1477.

EXAMPLE XVI

Obtaining the 3f Ligand

(92) ##STR00028##

(93) To a solution of 1,2,3,4-tetrahydroisoquinoline (1.332 g, 10.0 mmol, 1 molar eq.) and benzyl bromide (3.590 g, 21.0 mmol, 2.1 molar eq.) in acetonitrile (100 ml), K.sub.2CO.sub.3 (2.073 g, 15.0 mmol, 1.5 molar eq.) was added. The mixture was heated while boiling with vigorous stirring under reflux over 4 hours, then cooled, filtered and concentrated to dryness. Crude ammonium salt was dissolved in methylene chloride and excess ethyl acetate was added. Methylene chloride was slowly evaporated under reduced pressure. The precipitated product was filtered and washed with ethyl acetate. Ammonium salt was obtained in the form of white crystalline solid (3.880 g, 98%). The ammonium salt obtained in the preceding step was dissolved in ethanol (96%, 50 ml) and NaOH (0.590 g, 14.8 mmol, 1.5 molar eq.) was added. The mixture was heated while boiling with vigorous stirring over 2 hours, then ethanol was cooled and evaporated to obtain yellow oil, which was dissolved in methylene chloride and washed with water. The crude product was then dried over Na.sub.2SO.sub.4, filtered and evaporated to dryness to obtain a slightly yellow oil (2.605 g, 84%).

(94) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.56-7.52 (m, 1H), 7.50-7.46 (m, 1H), 7.43-7.39 (m, 4H), 7.38-7.34 (m, 4H), 7.31-7.25 (m, 4H), 7.05 (dd, J=17.4; 10.9 Hz, 1H), 5.64 (dd, J=17.4; 1.6 Hz, 1H), 5.25 (dd, J=10.9; 1.6 Hz, 1H), 3.64 (s, 2H), 3.57 (s, 4H).

(95) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=137.6, 136.4, 135.1, 130.3, 129.0, 128.1, 127.4, 127.2, 126.9, 125.6, 114.5, 58.2, 56.1, 26.9.

EXAMPLE XVII

Obtaining the 3g Ligand

(96) ##STR00029##

(97) To a solution of 1,2,3,4-tetrahydroisoquinoline (2.660 g, 20.0 mmol, 1 molar eq.) and 4-bromobenzyl bromide (10.500 g, 42.0 mmol, 2.1 molar eq.) in acetonitrile (100 ml), K.sub.2CO.sub.3 (4.150 g, 30.0 mmol, 1.5 molar eq.) was added. The mixture was heated while boiling with vigorous stirring under reflux over 6 hours, then cooled, filtered and concentrated to dryness, to obtain crude ammonium salt that was used in the next step without purification. The salt was dissolved in ethanol (96%, 100 ml) and NaOH (1.200 g, 30.0 mmol, 1.5 molar eq.) was added. The mixture was heated under reflux with vigorous stirring over 6 hours. Ethanol was cooled and evaporated to obtain yellow oil, which solidifies when stored. The resulting oil was dissolved in methylene chloride, washed with water and excess methanol was added, after which methylene chloride was slowly evaporated under reduced pressure. The precipitated product was filtered and washed with methanol. A product was obtained in the form of white crystalline solid (8.111 g, 86%).

(98) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.55-7.51 (m, 1H), 7.48-7.43 (m, 4H), 7.40-7.37 (m, 1H), 7.29-7.24 (m, 2H), 7.24-7.20 (m, 4H), 6.96 (dd, J=17.5; 10.9 Hz, 1H), 5.64 (dd, J=17.5; 1.5 Hz, 1H), 5.25 (dd, J=11.0; 1.5 Hz, 1H), 3.59 (s, 2H), 3.46 (s, 4H).

(99) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=138.2, 137.6, 135.8, 134.9, 131.2, 130.6, 130.2, 127.5, 127.4, 125.8, 120.8, 114.8, 57.4, 56.2.

(100) HRMS: ESI was calculated for C.sub.23H.sub.22Br.sub.2N [M+H].sup.+: 470.0114; found: 470.0106.

EXAMPLE XVIII

Obtaining the 3h Ligand

(101) ##STR00030##

(102) To a solution of 6,7-dimetoxy-1,2,3,4-tetrahydroisoquinoline hydrochloride (11.490 g, 50.0 mmol, 1 molar eq.) and benzyl bromide (21.38 g, 125.0 mmol, 2.5 molar eq.) in ethanol (96%, 250 ml), K.sub.2CO.sub.3 (24.190 g, 175.0 mmol, 3.5 molar eq.) was added. The mixture was heated while boiling with vigorous stirring under reflux over 4 hours, then cooled, filtered and concentrated to dryness. Acetone (100 ml) was then added and brought to boil and cooled, then filtered, washed with acetone and dried. Ammonium salt was obtained in the form of white crystalline solid (20.890 g, 92%). This was dissolved in ethanol (96%, 184 ml) and NaOH (4.600 g, 115.0 mmol, 2.5 molar eq.) was added. The mixture was heated while boiling with vigorous stirring over 6 hours, then ethanol was cooled and evaporated to obtain yellow oil, which solidifies when stored. The crude product was dissolved in diethyl ether, washed with water and excess heptane was added. Then diethyl ether was slowly evaporated under reduced pressure. The precipitated product was filtered and washed with heptane. A product was obtained in the form of white crystalline solid (11.580 g, 67%).

(103) .sup.1H NMR (CDCl.sub.3, 600 MHz): ?=7.41-7.37 (m, 4H), 7.36-7.30 (m, 4H), 7.28-7.22 (m, 2H), 7.05-6.94 (m, 3H), 5.53 (dd, J=17.5; 1.6 Hz, 1H), 5.17 (dd, J=11.0; 1.6 Hz, 1H), 3.94-3.88 (m, 6H), 3.57 (m, 6H).

(104) .sup.13C NMR (CDCl.sub.3, 150 MHz): ?=148.4, 147.9, 139.4, 134.4, 129.8, 129.3, 128.9, 128.1, 126.8, 113.0, 112.6, 108.2, 58.0, 55.9, 55.8, 55.3.

EXAMPLE XIX

RCM Reaction of Diethyl Diallylmalonate (S1)

(105) To the S1 solution (0.240 g, 1.0 mmol) in toluene (10 ml) in the predetermined temperature, the predetermined amount of the appropriate (pre)catalyst in toluene (50 ?l) was added in one portion. At adequate intervals, samples were taken of the reaction mixture to which 3 drops of ethyl vinyl ether were added to deactivate the catalyst. The samples were analysed by gas chromatography.

(106) ##STR00031##

(107) TABLE-US-00001 TABLE 1 Experimental results of the RCM reaction of diethyl diallylmalonate S1 at the temperature of 29? C. using 0.1 mol % (pre)catalysts. Conversion [%] Time [min] 1a 1b 1c 1d 1e 1f 1g 12a 12j C1 C3 C4 2 23 93 98 98 41 30 5 8 9 82 >99 >99 >99 72 63 10. 9 10. 99 91 90 20 10. 13 >99 98 99 30 11 18 99 >99 60 4 14 26 <1 >99 <1 <1

(108) TABLE-US-00002 TABLE 2 Experimental results of the RCM reaction of diethyl diallylmalonate S1 at the temperature of 29? C. using 200 ppm of (pre)catalysts (better differentiation of the fastest (pre)catalysts). Conversion [%] Time [min] 1d 1e 1f 1g 1h C5 1 14 24 35 33 24 14 2 24 48 67 66 47 24 5 66 93 >99 98 98 61 10. 95 >99 >99 99 86 20 >99 >99 94 30 96

(109) TABLE-US-00003 TABLE 3 Experimental results of the RCM reaction of diethyl diallylmalonate S1 at the temperature of 40? C. using 0.1 mol % (pre)catalysts. Conversion [%] Time [min] 1a 1b 1c 1d 1e 1f 12a 12i 12j C1 C2 C3 C4 2 9 9 >99 >99 >99 75 41 5 11 13 95 88 10. 13 18 >99 99 20 21 32 >99 30 29 46 60 14 45 73 <1 16 <1 13 <1

(110) TABLE-US-00004 TABLE 4 Experimental results of the RCM reaction of diethyl diallylmalonate S1 at the temperature of 80? C. using 0.1 mol % (pre)catalysts. Conversion [%] Time [min] 1a 1b 1c 12a 12i 12j C1 C2 C3 C4 2 30 52 71 20 >99 13 >99 5 84 95 99 51 18 10. 97 99 99 77 30 5 20 >99 >99 >99 13 88 19 43 13 30 91 47 23 60 24 94 33 52 46

EXAMPLE XX

CM Reaction of Methyl Acrylate with Ethyl Undecanoate (S2)

(111) To the S2 solution (1.062 g, 1.58 mmol, 1 molar eq.), acrylonitrile (0.655 ml, 10.0 mmol, 2 molar eq.) and methyl stearate (internal standard) in toluene (8.3 ml) at the temperature of 85? C. under argon, a solution of an appropriate (pre)catalyst (100 ppm) in toluene (50 ?l) was added, in one portion. The whole was stirred over 1 hour. During the reaction, a stream of argon was passed through the solution. A sample was taken to which 3 drops of ethyl vinyl ether were added to deactivate the catalyst. The sample was analysed by gas chromatography.

(112) ##STR00032##

(113) TABLE-US-00005 TABLE 5 Experimental results of the CM reaction of acrylonitrile with S2 (pre)catalyst Conversion P2 D2 Selectivity to P2 [Ru] [%] [%] [%] [%] 1a 91 84 7 92 1b 97 92 5 95 1c 96 90 6 94 1d 97 92 5 95 1e 94 89 5 95 1f 93 87 6 94 12a 17 16 1 94 12i 34 32 2 94 12j 26 24 2 92 C1 5 4 1 80 C2 55 46 9 84 C3 44 37 7 84 C4 21 16 5 76

EXAMPLE XXI

Homometathesis Reaction of Ethyl Undecanoate (S2)

(114) To S2 (3.00 g, 14.13 mmol) and methyl stearate (internal standard) at the temperature of 85? C. under argon, a solution of an appropriate (pre)catalyst (30 ppm) in toluene (50 ?l) was added, in one portion. The whole was stirred over 1 hour. During the reaction, a stream of argon was passed through the solution. A sample was taken to which 3 drops of ethyl vinyl ether were added to deactivate the catalyst. The sample was analysed by gas chromatography.

(115) ##STR00033##

(116) TABLE-US-00006 TABLE 6 Experimental results of the homodimerization reaction of S2. (pre)catalyst [Ru] Conversion [%] D2 [%] Selectivity to D2 [%] 1a 96 93 97 1b 95 92 97 1c 97 94 97 1d 71 69 97 1e 52 50 96 1f 48 47 97 12a 76 52 69 12i 99 67 68 12j 81 55 68 C1 51 43 84 C2 98 72 74 C3 96 65 68 C4 84 81 97 C5 53 51 97