USE OF N-CHELATING RUTHENIUM COMPLEXES IN THE METATHESIS REACTION

Abstract

The subject matter of the invention is the use of a ruthenium complex of the formula 1, wherein the individual substituents have meanings as indicated in the olefin metathesis reactions description, including a reaction selected from such as ring-closing metathesis (RCM), homometathesis (self-CM) or cross metathesis (CM).

##STR00001##

Claims

1. The use of a ruthenium complex of formula 1, ##STR00028## wherein: X.sup.1, X.sup.2 independently represent an anionic ligand selected from halogen atom, —OR, —SR, —C(C═O)R, where R represents 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 perfluoroalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom; R.sup.1 represents a hydrogen atom or C.sub.5-C.sub.24 aryl, C.sub.1-C.sub.25 alkyl, C.sub.4-C.sub.25 heteroaryl, C.sub.7-C.sub.24 aralkyl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, optionally C.sub.1-C.sub.12 perfluoroalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom, wherein the alkyl groups can be linked to each other to form a ring; R.sup.2 represents C.sub.5-C.sub.24 aryl, C.sub.4-C.sub.25 heteroaryl, C.sub.7-C.sub.24 aralkyl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, optionally C.sub.1-C.sub.12 perfluoroalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom, wherein the alkyl groups can be interconnected to form a cyclic system; a, b, c, d independently represent 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 can be linked to each other to form a ring; can also independently represent an alkoxy group (—OR′), thioether (—SR′), nitro (—NO.sub.2), cyano (—CN), amide (—CONR′R′), carboxyl and ester (—COOR′), sulfone (—SO.sub.2R′), sulfonamide (—SO.sub.2NR′R′), formyl and ketone (—COR′), in which the substituents R′ and R″ independently have the following meanings: 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; L represents a neutral ligand, such as a P(R′).sub.3 group, in which R′ independently represents C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.5-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, two substituents R′ can be interconnected to form a cycloalkyl ring containing a phosphorus atom in the ring, or L is selected independently from the group including the so-called N-heterocyclic carbene ligands of the formula 2a or 2b: ##STR00029## wherein: each R.sup.3 and R.sup.4 independently represent 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 with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.2-C.sub.12 alkoxy or a halogen atom; each R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 independently represents 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 with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy or a halogen atom, and R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 groups can be optionally interconnected to form a C.sub.4-C.sub.10 cyclic or C.sub.4-C.sub.12 polycyclic system; in olefin metathesis reactions including a reaction selected from such as ring-closing metathesis (RCM), homometathesis (self-CM) or cross metathesis (CM).

2. The use according to claim 1, in which in the formula 1 ##STR00030## X.sup.1 and X.sup.2 represent halogen atoms; L represents a P(R′).sub.3 group, where R′ represents C.sub.3-C.sub.8 cycloalkyl or L represents a ligand of formula 2a or 2b, in which substituents R.sup.3, R.sup.4, R, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 are as defined above; R.sup.1 represents a hydrogen atom or C.sub.5-C.sub.24 aryl, C.sub.4-C.sub.25 heteroaryl, C.sub.7-C.sub.24 aralkyl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, optionally C.sub.1-C.sub.12 perfluoroalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom, wherein the alkyl groups can be interconnected to form a cyclic system; R.sup.2 represents C.sub.5-C.sub.24 aryl, C.sub.4-C.sub.25 heteroaryl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, optionally C.sub.1-C.sub.12 perfluoroalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom, wherein the alkyl groups can be linked to each other to form a ring; a, b, c, d independently represent a hydrogen atom, an alkoxy (—OR′), thioether (—SR′), nitro (—NO.sub.2), cyano (—CN), amide (—CONR′R), carboxyl and ester (—COOR′), sulfone (—SO.sub.2R′), sulfonamide (—SO.sub.2NR′R′), formyl and ketone (—COR′) group, where the substituents R′ and R″ independently have the following meanings: 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 use according to claim 1, wherein in the formula 1 ##STR00031## X.sup.1 and X.sup.2 represent halogen atoms; represents a P(R′).sub.3 group, in which R′ represents C.sub.3-C.sub.8 cycloalkyl; or L represents a ligand of formula 2a, in which each R.sup.3 and R.sup.4 independently represent C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.2 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.2-C.sub.12 alkoxy, each R.sup.5, R.sup.6, R.sup.7, R.sup.8 independently represents 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 with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy or a halogen atom, and R.sup.5, R.sup.6, R.sup.7, R.sup.8 groups can be optionally interconnected to form a C.sub.4-C.sub.10 cyclic or C.sub.4-C.sub.12 polycyclic system; R.sup.1 represents a hydrogen atom or C.sub.5-C.sub.24 aryl, C.sub.4-C.sub.25 heteroaryl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, optionally C.sub.1-C.sub.12 perfluoroalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom, wherein the alkyl groups can be interconnected to form a cyclic system; R.sup.2 represents C.sub.5-C.sub.24 aryl, C.sub.4-C.sub.25 heteroaryl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, optionally C.sub.1-C.sub.12 perfluoroalkyl, optionally C.sub.1-C.sub.12 alkoxy, optionally a halogen atom, wherein the alkyl groups can be interconnected to form acyclic system; a, b, c, d independently represent a hydrogen atom, an alkoxy (—OR′), nitro (—NO.sub.2), amide (—CONR′R′), ester (—COOR′), sulfone (—SO.sub.2R′), sulfonamide (—SO.sub.2NR′R′) group, in which the substituents R′ and R″ independently have the following meanings: C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.24 aryl.

4. The use according to claim 1, wherein in the formula 1 ##STR00032## L represents a P(R′).sub.3 group, in which R′ represents C.sub.3-C.sub.8 cycloalkyl; or L represents a ligand of formula 2a, in which each R.sup.3 and R.sup.4 independently represent C.sub.5-C.sub.20 aryl, which is optionally substituted with at least one C.sub.1-C.sub.12 alkyl, and each R.sup.5, R.sup.6, R.sup.7, R.sup.8 independently represents a hydrogen atom; R.sup.1 represents a hydrogen atom or C.sub.5-C.sub.24 aryl, C.sub.4-C.sub.24 heteroaryl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, optionally a halogen atom, wherein the alkyl groups can be interconnected to form a cyclic system; R.sup.2 represents C.sub.5-C.sub.24 aryl or C.sub.4-C.sub.24 heteroaryl, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, optionally a halogen atom, wherein the alkyl groups can be interconnected to form a cyclic system; a, b, c, d independently represent a hydrogen atom, an alkoxy group (—OR′), in which the substituent R′ independently represents C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.24 aryl.

5. The use according to claim 1, wherein in the formula 1 ##STR00033## L represents tricyclohexylphosphine; or L represents a ligand of formula 2a, in which each R.sup.3 and R.sup.4 independently represent C.sub.1-C.sub.20 aryl, which is optionally substituted with at least one C.sub.1-C.sub.12 alkyl, and each R.sup.5, R.sup.6, R.sup.7, R.sup.8 independently represents a hydrogen atom; R.sup.1 represents a hydrogen atom, C.sub.5-C.sub.24 aryl or C.sub.4-C.sub.25 heteroaryl, which are optionally substituted with at least one a halogen atom; R.sup.2 represents C.sub.5-C.sub.24 aryl or C.sub.4-C.sub.25 heteroaryl, which are optionally substituted with at least one a halogen atom; a, b, c, d independently represent a hydrogen atom, an alkoxy group (—OR′), in which the substituent R′ independently represents C.sub.1-C.sub.25 alkyl.

6. The use according to claim 1, wherein the ruthenium complex of general formula 1 has a structure represented by a structural formula selected from the formulas 1a-1g ##STR00034## ##STR00035##

7. The use according to claim 1, wherein the reaction is carried out in an organic solvent such as toluene, benzene, mesitylene, dichloromethane, ethyl acetate, methyl acetate, tetrabutyl methyl ether, cyclopentyl methyl ether, or without a solvent.

8. The use according to claim 1, wherein the reaction is carried out at a temperature of from 0 to 150° C.

9. The use according to claim 1, wherein the reaction is carried out at a temperature of from 20 to 120° C.

10. The use according to claim 1, wherein the reaction is carried out for from 1 minute to 24 hours.

11. The use according to claim 1 wherein the compound 1 is used in an amount of not more than 0.5 mol %.

12. The use according to claim 1, wherein compound 1 is added to the reaction mixture in solid form and/or in the form of a solution in an organic solvent.

Description

EMBODIMENTS OF THE INVENTION

[0040] The following examples are only intended to illustrate the invention and to explain its particular aspects, without limitation, and should not be equated with its entire scope, which is defined in the appended claims. In the following examples, unless otherwise indicated, standard materials and methods used in the field were used or the manufacturers' recommendations for specific reagents and methods were followed.

[0041] The use of (pre)catalysts 1 was compared with (pre)catalysts C1-C3, structures of which are illustrated below:

##STR00014##

[0042] Diethyl malonate (S1), ethyl undecenoate (S3), acrylonitrile and methyl stearate are commercially available compounds. Diethyl (2,2-dimethylallyl)malonate (S2) was prepared according to the procedure from literature, S1 and S3 were distilled under reduced pressure and stored over activated alumina. Acrylonitrile was dried with 4 Å molecular sieves and deoxygenated with argon. All reactions were carried out under argon. Toluene was washed with citric acid, water, dried with 4A molecular sieves and deoxidized with argon.

[0043] The composition of the reaction mixtures was examined by gas chromatography using a PerkinElmer Clarus 680 GC apparatus equipped with a GL Sciences InertCap 5 MS/NP capillary column.

[0044] The individual components of the reaction mixtures were identified by comparing the retention times with commercial standards or isolated from reaction mixtures for which the structure was confirmed by NMR.

Example I

Application Example: RCM Reaction of Diethyl Diallylmalonate (S1)

[0045] To a solution of S1 (0.240 g, 1.0 mmol) in toluene (10 ml) at a designated temperature a determined amount of the corresponding (pre)catalyst in toluene (50 μl) was added in one portion. At appropriate intervals, samples of the reaction mixture were taken, to which 3 drops of ethyl vinyl ether were added to deactivate the catalyst. The samples were analyzed by gas chromatography.

##STR00015##

TABLE-US-00001 TABLE 1 Results of RCM reaction of diethyl diallylmalonate S1 at 29° C. using 0.1 mol % (pre)catalysts. Time Conversion [%] [min] 1b 1d 2 41 30 5 72 63 10 91 90 20 98 99 30 99 >99 60 >99 —

TABLE-US-00002 TABLE 2 Results of RCM reaction of diethyl diallylmalonate S1 at 40° C. using 0.1 mol % (pre)catalysts. Time Conversion [%] [min] C2 1a 1b 1c 1d 2 — — 75 — 41 5 — — 95 — 88 10 — — >99 — 99 20 — — — — >99 30 — — — — — 60 <1 16 — 13 —

TABLE-US-00003 TABLE 3 Results of RCM reaction of diethyl diallylmalonate S1 at 80° C. using 0.1 mol % (pre)catalysts. Time Conversion [%] [min] C2 1a 1b C1 1c 1d 1g 2 — 20 >99 — 13 >99 34 5 — 51 — — 18 — 66 10 — 77 — — 30 — 90 20 13 88 — 19 43 — 99 30 — 91 — — 47 — >99 60 24 94 — 33 52 — —

Example II

Application Example: RCM Reaction of (2,2-Dimethylallyl) Malonate (S2)

[0046] ##STR00016##

[0047] To a solution of S2 (0.240 g, 1.0 mmol) in toluene (10 ml) at a designated temperature a determined amount of the corresponding (pre)catalyst in toluene (50 μl) was added in one portion. At the appropriate time intervals, samples of the reaction mixture were taken, to which 3 drops of ethyl vinyl ether were added to deactivate the catalyst. The samples were analyzed by gas chromatography.

TABLE-US-00004 TABLE 4 Results of RCM reaction of (2,2-dimethylallyl) malonate (S2) at 80° C. using 0.5 mol % (pre)catalysts. Time Conversion [%] [min] C3 1e 30 91 93 60 93 94

TABLE-US-00005 TABLE 5 Results of RCM reaction of (2,2-dimethylallyl) malonate (S2) at 100° C. using 0.5 mol % (pre)catalysts. Time Conversion [%] [min] C3 1e 30 88 96 60 89 96

Example III

Application Example: RCM Reaction of Acrylonitrile with Ethyl Undecanoate (S3)

[0048] To a solution of S3 (1.062 g, 5.0 mmol, 1 molar equivalent), acrylonitrile (0.655 mL, 10.0 mmol, 2 molar equivalents) and methyl stearate (internal standard) in toluene (8.3 mL) at 85° C. under argon, a solution of the appropriate (pre)catalyst (100 ppm) in toluene (50 μl) was added in one portion. The reaction was stirred for 1 hour. A stream of argon was passed through the solution during the reaction. A sample was taken, into which 3 drops of ethyl vinyl ether were added to deactivate the catalyst. The sample was analyzed by gas chromatography.

##STR00017##

TABLE-US-00006 TABLE 6 Results of CM reaction of acrylonitrile with S3. (pre)catalyst Conversion P3 D3 Selectivity towards P3 [Ru] [%] [%] [%] [%] 1a 34 32 2 94 1b 26 24 2 92 1c 55 46 9 84 1d 44 37 7 84 C2 17 16 1 94

Example IV

Application Example: Homometathesis of Ethyl Undecenoate (S3)

[0049] To S3 (3.00 g, 14.13 mmol) and methyl stearate (internal standard) at 85° C. under argon a solution of the appropriate (pre)catalyst (30 ppm) in toluene (50 μl) was added in one portion. The reaction was stirred for 1 hour. A stream of argon was passed through the solution during the reaction. A sample was taken, into which 3 drops of ethyl vinyl ether were added to deactivate the catalyst. The sample was analyzed by gas chromatography.

##STR00018##

TABLE-US-00007 TABLE 7 Results of homodimerization reaction of S3. (pre)catalyst Conversion D3 Selectivity towards D3 [Ru] [%] [%] [%] 1a 99 67 68 1b 81 55 68 1c 98 72 74 1d 96 65 68 C2 76 52 69 C1 51 43 84

[0050] The C1-C2 (pre)catalysts known in the state of the art initiate the metathesis reaction of S3 without the addition of an activator, while their activity is significantly lower than (pre)catalysts 1a-d.

Example V

Synthesis of Complex 1a.

[0051] ##STR00019##

[0052] To the Gru-II complex (2.000 g, 2.36 mmol, 1 molar equivalent) dry deoxygenated toluene (23 ml), benzylidene ligand 9a (0.615 g, 2.59 mmol, 1.1 molar equivalent) and CuCl (0.350 g, 3.53 mmol, 1.2 molar equivalent) was added under argon. The reaction was stirred for 20 minutes at 55° C. Than was cooled to room temperature and concentrated to dryness. The residue was dissolved in ethyl acetate, filtered through a pad of Celite and concentrated to dryness. The crude product was isolated using 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 of heptane was added. Methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered and washed with cold heptane to give a green crystalline solid—(pre)catalyst 1a (1.340 g, 81%).

[0053] .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): δ=18.70 (s, 1H), 7.50 (t. J=7.5 Hz. 1H), 7.31-7.23 (m, 3H), 7.19 (t, J=7.4 Hz. 1H), 7.05 (br s, 4H), 6.99 (br s, 2H), 6.90 (d, J=7.5 Hz, 1H), 6.74 (d, J=7.3 Hz, 1H), 4.10 (s, 4H), 3.90-3.00 (br m, 3H), 2.90-2.00 (br m, 19H), 1.73 (s, 3H).

[0054] .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): δ=313.4, 313.3, 213.4, 148.9, 139.0, 134.0, 132.6, 132.5, 131.6, 129.8, 129.1, 129.0, 128.4, 128.3, 127.3, 60.0, 43.1, 32.4, 29.6, 23.3, 21.4, 14.4.

[0055] HRMS: ESI was calculated for C.sub.37H.sub.43N.sub.3Ru [M-2Cl].sup.2+: 315.6250; found: 315.6247. (dimer)

Example VI

Synthesis of Complex 1

[0056] ##STR00020##

[0057] To the M2 complex (1.25 g, 2.36 mmol, 1 molar equivalent) dry deoxygenated toluene (13 ml), benzylidene ligand 9b (0.495 g, 1.58 mmol, 1.2 molar equivalent) and CuCl (0.183 g, 1.84 mmol, 1.4 molar equivalent) was added under argon. The reaction was stirred for 30 minutes at 70° C. Than was cooled to room temperature and concentrated to dryness. The residue was dissolved in ethyl acetate, filtered through a pad of Celite and concentrated to dryness. The crude product was isolated using 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 of heptane was added. Methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered and washed with cold heptane to give a green crystalline solid—(pre)catalyst 1b (0.490 g, 48%).

[0058] .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): δ=18.61 (s, 1H), 7.60-6.30 (m, 18H), 4.60-1.50 (m, 28H).

[0059] .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): δ=315.3, 213.2, 149.5, 139.0, 135.4, 134.6, 132.3, 131.0, 129.9, 129.1, 127.9, 127.8, 126.1, 58.8, 34.7, 22.9, 21.3, 14.4.

[0060] HRMS: ESI was calculated for C.sub.43H.sub.47N.sub.3ClRu [M-Cl].sup.+: 742.2502; found: 742.2493.

Example VII

Synthesis of Complex 1c

[0061] ##STR00021##

[0062] To the M20-SIPr complex (2.00 g, 1.97 mmol, 1 molar equivalent) dry deoxygenated toluene (19 ml), benzylidene ligand 9a (0.468 g, 1.97 mmol, 1.0 molar equivalent) and CuCl (0.293 g, 2.96 mmol, 1.5 molar equivalent) was added under argon. The reaction was stirred for 30 minutes at 80° C. Than was cooled to room temperature and concentrated to dryness. The residue was dissolved in ethyl acetate, filtered through a pad of Celite and concentrated to dryness. The crude product was isolated using 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 of heptane was added. Methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered and washed with cold heptane to give a green crystalline solid—(pre)catalyst 1c (0.470 g, 30%).

[0063] .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): δ=18.61 (s, 1H), 7.70-6.70 (m, 14H), 6.57 (d, J=7.7 Hz, 1H), 4.80-2.30 (br m, 11H), 2.20-0.20 (br m, 28H).

[0064] .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): δ=307.0, 215.5, 149.6, 148.1, 133.9, 132.7, 131.5, 129.9, 128.9, 128.7, 128.4, 128.3, 127.5, 124.9, 60.1, 55.1, 43.6, 29.2, 27.0, 23.9.

[0065] HRMS: ESI was calculated for C.sub.45H.sub.58N.sub.4ClRu [M-Cl+CH.sub.3CN].sup.+: 791.3397; found: 791.3391.

Example VIII

Synthesis of Complex 1d

[0066] ##STR00022##

[0067] To the M20-SIPr complex (0.500 g, 0.49 mmol, 1 molar equivalent) dry deoxygenated toluene (5 mL), benzylidene ligand 9b (0.185 g, 0.59 mmol, 1.2 molar equivalent) and CuCl (0.059 g, 0.59 mmol, 1.2 molar equivalent) was added under argon. The reaction was stirred for 20 minutes at 60° C. It was cooled to room temperature and concentrated to dryness. The residue was dissolved in ethyl acetate, filtered through a pad of Celite and concentrated to dryness. The crude product was isolated using 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 of heptane was added. Methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered and washed with cold heptane to give a green crystalline solid—(pre)catalyst 1d (0.083 g, 20%).

[0068] .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): δ=18.33 (s, 1H), 7.80-6.95 (m, 12H), 6.95-6.30 (m, 7H), 6.05 (d, J=7.7 Hz, 1H), 4.60-2.60 (br m, 14H), 2.0-0.20 (br m, 24H).

[0069] .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): δ=311.0, 215.6, 148.6, 135.9, 132.8, 132.6, 130.0, 129.6, 128.6, 127.4, 127.4, 126.9, 126.4, 124.4, 62.2, 59.3, 57.4, 55.7, 32.4, 29.6, 27.8, 26.4, 23.7, 23.3, 14.4.

Example IX

Synthesis of Complex 1e

[0070] ##STR00023##

[0071] To the o-Tollyl compound (0.300 g, 1.04 mmol, 1.5 molar equivalent) dry deoxygenated toluene (5 mL) was added, placed in an oil bath heated to 45° C. and then LiHMDS (1 mL, 1.04 mmol, 1.5 molar equivalent) was added. After 5 minutes of reaction, 1g (0.522 g, 0.69 mmol, 1 molar equivalent) and CuCl (0.103 g, 1.04 mmol, 1.5 molar equivalent) were added under argon. The reaction was stirred for 20 minutes at 45° C. It was cooled to room temperature and concentrated to dryness. The residue was dissolved in ethyl acetate, filtered through a pad of Celite and concentrated to dryness. The crude product was isolated using 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 of heptane was added. Methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered and washed with cold heptane to give a green crystalline solid—(pre)catalyst 1e (0.274 g, 55%).

[0072] ESI was calculated for C.sub.39H.sub.39N.sub.3ClRu [M-Cl].sup.+: 686.1878; found: 686.1884.

Synthesis of Complex 1f

[0073] ##STR00024##

[0074] To the Alk-I complex (1.00 g, 1.25 mmol, 1 molar equivalent) dry deoxygenated methylene chloride (12 ml), benzylidene ligand 9a (0.356 g, 1.50 mmol, 1.2 molar equivalent) and CuCl (0.148 g, 1.50 mmol, 1.2 molar equivalent) was added under argon. The reaction was stirred for 20 minutes at 35° C. It was cooled to room temperature and concentrated to dryness. The residue was dissolved in ethyl acetate, filtered through a pad of Celite and concentrated to dryness. The residue was dissolved in methylene chloride and excess methanol was added. Methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered and washed with cold methanol to give a green crystalline solid—(pre)catalyst 1f (0.592 g, 70%).

[0075] .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): δ=19.15 (s, 1H), 7.90-6.70 (m, 9H), 4.45-4.05 (m, 2H), 2.40-2.26 (m, 3H), 2.12-1.90 (m, 8H), 1.88-1.58 (m, 16H), 1.36-1.16 (m, 11H).

[0076] .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): δ=295.5, 148.2, 134.3, 133.2, 132.8, 132.4, 129.9, 129.1, 128.7, 128.6, 126.5, 63.1, 43.8, 35.2 (d, J=20.3 Hz), 30.7, 28.5 (d, J=10.0 Hz), 27.0, 26.9.

[0077] .sup.31P NMR (CD.sub.2Cl.sub.2, 243 MHz): δ=35.6.

Example XI

Synthesis of Complex 1q

[0078] ##STR00025##

[0079] To the Alk-I complex (1.00 g, 1.25 mmol, 1 molar equivalent) dry deoxygenated methylene chloride (12 ml), benzylidene ligand 9b (0.470 g, 1.50 mmol, 1.2 molar equivalent) and CuCl (0.148 g, 1.50 mmol, 1.2 molar equivalent) was added under argon. The reaction was stirred for 20 minutes at 35° C. It was cooled to room temperature and concentrated to dryness. The residue was dissolved in ethyl acetate, filtered through a pad of Celite and concentrated to dryness. The residue was dissolved in methylene chloride and excess methanol was added. Methylene chloride was slowly removed under reduced pressure. The resulting precipitate was filtered and washed with cold methanol to give a green crystalline solid—(pre)catalyst 1g (0.592 g, 63%).

[0080] .sup.1H NMR (CD.sub.2Cl.sub.2, 600 MHz): δ=19.14 (d, J=10.2 Hz, 1H), 8.00-6.80 (m, 14H), 4.33 (d, J=14.0 Hz, 2H), 4.20-2.90 (br m, 2H), 2.39-2.26 (m, 3H), 2.05-1.60 (m, 22H), 1.38-1.16 (m, 10H).

[0081] .sup.13C NMR (CD.sub.2Cl.sub.2, 150 MHz): δ=297.7, 148.9, 134.6, 133.0, 132.7, 129.6, 129.2, 128.6, 126.6, 60.2, 34.8 (d, J=20.3 Hz), 30.2, 28.5 (d, J=9.8 Hz), 27.0.

[0082] .sup.31P NMR (CD.sub.2Cl.sub.2, 243 MHz): δ=34.5.

Example XII

Synthesis of Ligand 9a

[0083] ##STR00026##

[0084] To the solution of 1,2,3,4-tetrahydroisoquinoline (26.600 g, 200.0 mmol, 2 molar equivalents) and triethylamine (10.120g, 100.0 mmol, 1 molar equivalent) in methylene chloride (500 ml) cooled to 0° C. benzyl bromide (17.100 g, 100.0 mmol, 1 molar equivalent) was added dropwise for 10 minutes. [The mixture] was slowly warmed to room temperature and stirred overnight. It was washed with water and dried over Na.sub.2SO.sub.4. It was filtered and evaporated. It was distilled under reduced pressure. The product was collected in a fraction with a boiling point of 126-132° C. at a pressure of 1.1×10−2 mbar (colorless oil, 18.470 g, 83%).

[0085] .sup.1H NMR (CDCl.sub.3, 600 MHz): δ=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).

[0086] .sup.13C NMR (CDCl.sub.3, 150 MHz): δ=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.

[0087] HRMS: ESI was calculated for C.sub.16H.sub.18N [M+H].sup.+: 224.1434; found: 224.1441.

[0088] To the amine, obtained in the previous step, (12.946 g, 58.0 mmol, 1 molar equivalent) in ethanol (96%, 150 ml) methyl iodide (16.460 g, 116.0 mmol, 2 molar equivalents) was added. It was stirred at 35° C. overnight. The excess of methyl iodide was evaporated under reduced pressure. NaOH (3.480 g, 87.0 mmol, 1.5 molar equivalents) was added. It was heated in reflux with condenser vigorously stirring overnight. It was cooled and concentrated to dryness. The residue was dissolved in methylene chloride, washed with water and dried over Na.sub.2SO.sub.4. Filtered and concentrate to dryness. The crude product was filtered through a thin pad of silica gel (eluent:ethyl acetate/cyclohexane 5:95). Concentrated to dryness to give a colorless oil—ligand 9a (12.711 g, 92%).

[0089] .sup.1H NMR (CDCl.sub.3, 600 MHz): δ=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).

[0090] .sup.13C NMR (CDCl.sub.3, 150 MHz): δ=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.

[0091] HRMS: ESI was calculated for C.sub.17H.sub.20N [M+H]: 238.1590; found: 238.1596.

Example XIII

Preparation of Ligand 9b

[0092] ##STR00027##

[0093] To a solution of 1,2,3,4-tetrahydroisoquinoline (1.332 g, 10.0 mmol, 1 molar equivalent) and benzyl bromide (3.590 g, 21.0 mmol, 2.1 molar equivalents) in acetonitrile (100 mL) was added K.sub.2CO.sub.3 (2.073 g, 15.0 mmol, 1.5 molar equivalents). It was heated under reflux with condenser vigorously stirring for 4 hours. It was cooled, filtered and concentrated to dryness. The 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. The ammonium salt was obtained as a white crystalline solid (3.880 g, 98%). The ammonium salt obtained in the previous step was dissolved in ethanol (96%, 50 ml) and NaOH (0.590 g, 14.8 mmol, 1.5 molar equivalent) was added. It was heated in reflux with stirring for 2 hours. The mixture was cooled and methanol was evaporated, yielding a yellow oil. It was dissolved in methylene chloride, washed with water. It was dried over Na.sub.2SO.sub.4, filtered and concentrated to dryness to give a slightly yellow oil (2.605 g, 84%).

[0094] .sup.1H NMR (CDCl.sub.3, 600 MHz): δ=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).

[0095] .sup.13C NMR (CDCl.sub.3, 150 MHz): δ=139.4, 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.