Olefin metathesis catalysts

Abstract

The present invention refers to novel ruthenium-based catalysts for olefin metathesis reactions, particularly to fast initiating catalysts having stereoselective properties. In olefin metathesis reactions, the disclosed catalysts provide a high catalytic activity combined with the capability to generate higher yields of the olefin metathesis product.

Claims

1. A compound having the general Formula (I): ##STR00020## wherein L is an N-heterocyclic carbene ligand, L.sup.1 is pyridine, that may optionally be substituted with one or more substituents, NCO, CN, CNO, NCS, N.sub.3, X is halide, NCO, CN, CNO, NCS, or N.sub.3, R.sup.1 and R.sup.2 are independently selected from the group consisting of H, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.2-20 alkynyl, C.sub.1-20 alkoxy, C.sub.2-20 alkenyloxy, C.sub.5-14 aryl, C.sub.5-14 heteroaryl, C.sub.6-14 aryloxy, C.sub.6-14 heteroaryloxy, C.sub.1-20 alkylcarboxylate, C.sub.2-20 alkoxycarbonyl, C.sub.1-20 alkylthio, C.sub.1-20 alkylsufinyl and C.sub.1-20 alkylsulfonyl, each optionally substituted with one or more substituents, or R.sup.1 and R.sup.2 are covalently linked to form a 5- or 6-membered carbocyclic ring that may optionally be part of a bicyclic molecule and which may optionally be substituted with one or more substituents, R.sup.3 and R.sup.3 are independently 5- or 6-membered aromatic or heteroaromatic rings selected from the group consisting of phenyl, thiophenyl, furanyl, pyridinyl, imidazolinyl, pyranyl, thiopyranyl, pyrrolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazol and isothiazol, that may optionally be substituted with one or more substituents R.sup.4, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.2-20 alkynyl, C.sub.1-20 alkoxy, C.sub.2-20 alkenyloxy, C.sub.6-14 aryl, C.sub.6-14 heteroaryl, C.sub.6-14 aryloxy, C.sub.6-14 heteroaryloxy, C.sub.1-20 alkylcarboxylate, C.sub.2-20 alkoxycarbonyl, C.sub.1-20 alkylthio, C.sub.1-20 alkylsulfinyl and C.sub.1-20 alkylsulfonyl, each optionally substituted with one or more substituents, and no more than three of R.sup.3, R.sup.3, R.sup.4, R.sup.4 and R.sup.5 are H.

2. The compound of claim 1, wherein L is selected from the group consisting of imidazol-2-ylidenes, dihydroimidazol-2-ylidenes, triazol-5-ylidenes, tetrazol-5-ylidenes, pyrazol-3-ylidenes, benzimidazol-2-ylidenes, oxazol-2-ylidenes, thiazol-2-ylidenes and cyclic alkyl amino carbenes that may optionally be substituted at one or more ring atoms, wherein the substituents at one or both ring atoms neighbouring the carbene C-atom of L are independently selected from C.sub.1-6 alkyl groups and 5- or 6-membered aromatic or heteroaromatic rings that may optionally be substituted with one or more substituents, and wherein substituents at ring positions of L not neighbouring the carbene C-atom are independently selected from linear or branched C.sub.1-6 alkyl groups.

3. The compound of claim 1, wherein L is substituted at one or both ring atoms neighbouring the carbene C-atom and optionally at one or more additional ring atoms.

4. The compound of claim 1, wherein L is imidazol-2-ylidene, substituted at one or both N-atoms neighbouring the carbene C-atom and/or at one or both ring C-atoms.

5. The compound of claim 2, wherein both atoms neighbouring the carbene C-atom of L are substituted with phenyl groups that may in turn be substituted with one or more substituents.

6. The compound of claim 1, wherein substituents at ring positions of L not neighbouring the carbene C-atom are independently selected from linear or branched C.sub.1-6 alkyl groups.

7. The compound of claim 1, wherein one of R.sup.1 and R.sup.2 is H and the other is a 5- or 6-membered aromatic or heteroaromatic ring selected from the group consisting of phenyl, thiophenyl, furanyl, pyridinyl, imidazolinyl, pyranyl, thiopyranyl, pyrrolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazol and isothiazol, that may optionally be substituted with one or more substituents.

8. The compound of claim 1, wherein R.sup.1 and R.sup.2 are covalently linked to form a 1H-indene-1-ylidene group, optionally substituted with a phenyl group.

9. The compound of claim 1, wherein R.sup.4 and R.sup.4 are H and/or wherein R.sup.5 is H, phenyl or anthracenyl, optionally substituted with one or more substituents.

10. The compound of claim 1, wherein substituents at R.sup.3, R.sup.3, R.sup.4, R.sup.4 and R.sup.5 are independently selected from the group consisting of C.sub.1-6 alkyl, phenyl and CF.sub.3.

11. A catalyst for catalysing olefin metathesis reactions comprising a compound of claim 1, wherein the olefin metathesis reaction comprises a reaction selected from ring-closing metathesis, ring-opening metathesis, cross-metathesis, and ring opening metathesis polymerization.

12. The catalyst of claim 11 which is in free form or bound to a support.

13. The compound of claim 5, wherein one of R.sup.1 and R.sup.2 is H and the other is a 5- or 6-membered aromatic or heteroaromatic ring selected from the group consisting of phenyl, thiophenyl, furanyl, pyridinyl, imidazolinyl, pyranyl, thiopyranyl, pyrrolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazol and isothiazol, that may optionally be substituted with one or more substituents.

14. The compound of claim 6, wherein one of R.sup.1 and R.sup.2 is H and the other is a 5- or 6-membered aromatic or heteroaromatic ring selected from the group consisting of phenyl, thiophenyl, furanyl, pyridinyl, imidazolinyl, pyranyl, thiopyranyl, pyrrolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazol and isothiazol, that may optionally be substituted with one or more substituents.

15. The compound of claim 9, wherein substituents at R.sup.3, R.sup.3, R.sup.4, R.sup.4 and R.sup.5 are independently selected from the group consisting of C.sub.1-6 alkyl, phenyl and CF.sub.3.

16. The compound of claim 1, wherein R.sup.3 and R.sup.3 are phenyl, optionally substituted with one or more substituents.

17. A method for catalysing olefin metathesis reactions comprising combining a compound of claim 1 with an olefin, wherein the olefin metathesis reaction comprises a reaction selected from ring-closing metathesis, ring-opening metathesis, cross-metathesis, and ring opening metathesis polymerization.

18. The method of claim 17, wherein the compound of claim 1 is capable of stereoselectively generating disubstituted olefinic products.

19. The method of claim 17, wherein the compound of claim 1 is in free form or bound to a support.

Description

FIGURES

(1) FIG. 1 shows exemplary compounds of formula (I).

(2) FIG. 2 shows the Lewis structure of comparative catalysts D1-4d described in references 27, 28 and 47 and D2-4a described in references 32 and 48.

EXPERIMENTAL

(3) All reactions were performed under dry argon atmosphere, either inside a glovebox or using Schlenk techniques, unless otherwise stated. Tetrahydrofuran, toluene, and hexane, were purified using an MBraun solvent purification system (Grubbs' column). Tetrahydrofuran was dried overnight over KH and filtered through celite before use. Anhydrous pentane was purchased from Sigma-Aldrich and used as received. Pyridine was purchased from Sigma-Aldrich and degassed before use.

(4) CDCl.sub.3 was dried over CaH.sub.2 and distilled before use, while anhydrous C.sub.6D.sub.6 was purchased from Sigma-Aldrich and degassed before use. Allylacetate, allyl boronic acid pinacol ester, allylbenzene, 1-octene, 4-phenyl-1-butene,

(5) N-allylaniline, 2-(allyloxy)-ethanol, 10-undecenoic acid, and 4-pentenoic acid were purchased from Sigma-Aldrich and degassed before use. Allylbenzene and 2-(allyloxy)-ethanol were additionally dried over molecular sieves 4 and passed through a column of activated basic alumina respectively before use. The aryl thiols, 2,4,6-Triphenylbenzenethiol (1a) 2,6-diphenyl-4-(9-anthracenyl)benzenethiol (1e), 2,4,6-tris(3,5-dimethylphenyl)benzenethiol (1f), and 2,4,6-tris(3,5-ditertbutylphenyl)benzenethiol (1g) were purchased from Santai Labs and used as received. The ruthenium catalyst catMETium RF3 (3) was kindly supplied by Evonik Industries. Basic alumina (Sigma-Aldrich) was heated was heated for 60 hours at 220 C. under vacuum before use. All the other chemicals were purchased from Sigma-Aldrich and used as received.

(6) The ruthenium catalysts 6 (43), 8 (44), and 12 (45), and the dienes 22 (24) and 24 (24) used for testing ring closing metathesis were prepared according to literature procedure.

(7) Potassium 2,4,6-Triphenylbenzenethiolate 2a was prepared according to literature procedure (32), while the potassium thiolates 2e, 2f, and 2g were prepared using the following procedure: In a glovebox, KH (1.43 mmol) was added in small portions to a stirred solution of the corresponding thiol (i.e. 2,6-diphenyl-4-(9-anthracenyl)benzenethiol (1e), 2,4,6-tris(3,5-dimethylphenyl)benzenethiol (1f), and 2,4,6-tris(3,5-ditertbutylphenyl)benzenethiolate (1g) (1.36 mmol)) in THF (5 mL). The mixture was stirred at room temperature for 24 hours, the solvent removed under reduced pressure and the residue was washed three times with pentane, isolated over a frit and dried in the glove box. The quality of the product was evaluated by .sup.1H-NMR spectroscopy, which showed the disappearance of the thiol proton peak at 3.64 (2e), 3.55 (2f), and 3.59 (2g) ppm (CDCl.sub.3) respectively. The ruthenium complex 4 was prepared according the procedure described below.

(8) Preparation of Ruthenium Complex 4

(9) ##STR00004##

(10) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 3 (1087 mg, 1.234 mmol) and pyridine (4 mt). The vial was closed and the mixture stirred at room temperature for 1 hour. Then pentane (5 mL) was added to the reaction mixture causing the precipitation of a green solid. The solid was allowed to sediment (settle out) and then was isolated by vacuum filtration through a frit, washed three times with 5 mL of pentane and dried in the glovebox to give 786 mg (84% of yield). 1H NMR (600.17 MHz, C.sub.6D.sub.6): =19.10 (s, 1H), 9.15 (s, 2H), 8.69 (s, 2H), 7.76 (br s, 1H), 7.42 (d, J=4.8, 1 H), 6.83 (br t, J=6.7, 1 H), 6.76-6.44 (br m, 7 H), 6.38 (br t, J=6.7, 1 H), 6.18-6.03 (br m, 2H), 2.50 (br s, 12H), 2.07 (br s, 6 H), 1.51 (s, 6 H). .sup.13C{.sup.1H} NMR (150.91 MHz, C.sub.6D.sub.6): =289.11, 182.49, 164.83, 152.62, 150.88, 138.38, 135.83, 135.21, 134.29, 132.81, 130.08, 129.38, 128.35, 127.18, 122.92, 122.62, 21.16, 19.85 (br), 9.46.

(11) NMR spectra were recorded on Bruker Biospin AV 500, AV 600, and AV III HD 850 spectrometers. The chemical shifts are reported relative to the residual solvent peaks. (46) Elemental analyses were performed using an Elementar Vario EL III analyzer. The DART mass spectrum was recorded by means of a DART-100 ion source from IonSense Inc. (Saugus, Mass., USA) interfaced to an AccuTOF atmospheric ionization mass spectrometer from JEOL USA, Inc. (Peabody, Mass., USA). The AccuTOF mass spectrometer was operated with an orthogonal electrospray ionization source (ESI), an orthogonal accelerated time of flight (TOF) single stage reflectron mass analyzer and a dual micro channel plate (MCP) detector.

EXAMPLE 1

(12) Preparation of Ruthenium Complex 5e

(13) ##STR00005##

(14) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 4 (100 mg, 0.132 mmol), potassium 2,6-diphenyl-4-(9-anthracenyl)benzenethiolate (68 mg, 0.143 mmol) 2e and tetrahydrofuran (5 mL). After the addition of the solvent the color of the suspension changed rapidly from green to brown. The mixture was stirred at room temperature for 18 hours, and then filtered through a short pad of celite. The solvent was reduced to about 2 mL under reduced pressure and then 20 mL of pentane were slowly added to the filtrate and the mixture was placed in the freezer (32 C.) for a couple of days. The yellow-brown solid was isolated and further purified by repeating three times the following procedure: the solid was dissolved in about 2 mL of tetrahydrofuran followed by a slowly addition of about 20 mL of pentane. The mixture was placed in the freezer (32 C.) for a couple of days, and the yellow-brown solid was isolated and washed three times with pentane. After the above described procedure the solid was dried in the glove box to give 62 mg (43%) of the title compound 5e. .sup.1H NMR (600.17 MHz, C.sub.6D.sub.6): =17.26 (br s, 0.98 H), 17.09 (br s, 0.02 H), 8.67-5.75 (br m, 24 H), 8.17 (s, 1 H), 7.81 (d, J=8.9, 4H), 6.75 (t, J=7.5, 2 H), 6.30 (t, J=6.3, 2 H), 3.31-1.48 (br m, 18 H), 1.40 (s, 6 H). .sup.13C{.sup.1H} NMR (150.91 MHz, C.sub.6D.sub.6): =260.92 (br m), 179.01 (br), 154.72, 149.98 (br), 149.12 (br), 144.54 (br), 142.76, 138.20 (br), 137.87, 137.41, 135.12, 134.39, 134.06, 132.80, 131.89, 130.45 (br), 130.02, 129.69, 127.59, 126.63, 125.94, 125.14, 122.70, 21.45, 19.95 (br), 9.16. Elemental analysis, calculated for C.sub.65H.sub.58ClN.sub.3RuS.sub.2: C, 72.16; H, 5.40; N, 3.88; found: C, 72.51; H, 5.39; N, 3.82.

EXAMPLE 2

(15) Preparation of Ruthenium Complex 5f

(16) ##STR00006##

(17) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 4 (100 mg, 0.132 mmol), potassium 2,4,6-tris(3,5-dimethylphenyl)benzenethiolate (65 mg, 0.141 mmol) 2f, and tetrahydrafuran (5 mL). After the addition of the solvent the color of the suspension changed rapidly from green to reddish-brown. The mixture was stirred at room temperature for 1 hour. The solvent was reduced to about 1 mL under reduced pressure. Then 10 mL of pentane were added and the resulting dark-brown mixture was rapidly filtered through a glass-fiber filter paper. The filtrate was placed in the freezer (32 C.) for a couple of days. The red-brown solid was isolated, washed three times with pentane and dried in the glove box to give 99 mg (71%) of the title compound 5f. .sup.1H NMR (600.17 MHz, C.sub.6D.sub.6): =17.71 (br s, 0.47 H), 17.15 (br s, 0.53 H), 8.53 (br d, J=4.0, 1.04 H), 8.02-7.78 (br m, 1.35 H), 7.54 (d, J=4.8, 0.46 H), 7.46-7.25 (m, 2.60 H), 7.07-6.44 (m, 11.42 H), 6.33-5.98 (br m, 1.53 H), 2.81 (s, 1.32 H), 2.52-2.32 (br m, 16.34 H), 2.25 (br s, 1.59 H), 2.17 (br s, 2.62 H), 2.09 (s, 6.89 H), 2.03 (s, 2.94), 1.58 (br s, 2.20), 1.50 (br s, 1.40 H), 1.40 (br s, 1.52 H), 1.32 (s, 3.50 H). .sup.13C{.sup.1H} NMR (150.91 MHz, C.sub.6D.sub.6): =260.62, 184.84, 175.19, 165.09, 153.92, 152.01, 145.52, 143.76, 141.40, 141.27, 139.40, 138.83, 138.63, 138.35, 138.07, 138.01, 137.70, 137.04 (br), 136.83, 136.39, 136.17 (br) 135.80, 135.17, 134.12 (br), 134.05, 133.96, 133.63 (br), 129.93 (br), 129.64, 129.29, 129.17 (br), 129.11 (br), 128.94 (br), 128.67, 128.35, 124.98, 124.73, 123.48, 122.38, 30.49, 30.22, 22.02 (br), 21.78 (br), 21.56, 21.51, 21.42, 21.35, 21.10, 20.41, 19.98, 19.64, 19.77, 17.88, 9.17, 9.02, 8.94. Elemental analysis, calculated for C.sub.63H.sub.66ClN.sub.3RuS.sub.2: C, 70.99; H, 6.24; N, 3.94; found: C, 71.21; H, 5.91; N, 3.76. HRMS (DART): calculated for C.sub.58H.sub.62.sup.35ClN.sub.2.sup.102RuS.sub.2 [Mpy+H].sup.+: m/z=987.30864, found: m/z=987.30990.

EXAMPLE 3

(18) Preparation of Ruthenium Complex 5g

(19) ##STR00007##

(20) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 4 (100 mg, 0.132 mmol) and potassium 2,4,6-tris(3,5-ditertbutylphenyl)benzenethiolate (105 mg, 0.147 mmol) 2g, and tetrahydrofuran (3 mL). After the addition of the solvent the color of the suspension changed rapidly from green to dark red-brown. The mixture was stirred at room temperature for 1 hour. The solvent removed under reduced pressure, the residue extracted with pentane and filtered through a glass-fiber filter paper. The dark brown filtrate was then placed in the freezer (32 C.) for one week. The microcrystalline brown solid was isolated, washed with cold pentane, and dried in the glove box to give 95 mg (55%) of the title compound 5g. .sup.1H NMR (600.17 MHz, C.sub.6D.sub.6): =18.95 (br s, 0.2 H), 17.35 (br s, 0.8 H), 8.54 (br m, 1.6 H), 8.34 (br s, 0.2 H), 8.14 (s, 1.6 H), 7.89 (s, 0.8 H), 8.05-7.94 (br m, 0.4 H), 7.69 (d, J=4.7, 0.8 H), 7.64-7.55 (br m, 2.6 H), 7.52 (s, 0.8 H), 7.49-7.37 (br m, 1.4 H), 7.31-7.26 (br m, 1.6 H), 7.10 (br m, 0.2 H), 7.03 (s, 1.6 H), 7.00-6.94 (br m, 0.8 H), 6.91 (s, 0.8 H), 6.86-6.77 (br m, 1.4 H), 0.6.76-6.47 (br m, 5.8 H), 6.37 (br t, J=6.2, 0.4 H), 6.26 (s, 0.4 H), 2.63-1.89 (br m, 18 H), 1.60-1.44 (br m, 27 H), 1.38-1.17 (br m, 27 H), 1.04-0.82 (br m, 6 H). Elemental analysis, calculated for C.sub.81H.sub.102ClN.sub.3RuS.sub.2. C.sub.5H.sub.12: C, 74.28; H, 8.26; N, 3.02; found: C, 74.05; H, 8.14; N, 3.03.

EXAMPLE 4

(21) Dissociation of the Pyridine Ligand from Complexes 5e, 5f, and 5g in Benzene-d.sub.6 Solution

(22) ##STR00008##

(23) In a glove box, a NMR tube was charged with 0.5 mL of a benzene-d.sub.6 solution of the 16-electron ruthenium complex (A), capped and wrapped with a layer of parafilm. The percentage of the 14-electron complex (B), which is formed upon the dissociation of the pyridine ligand (L.sup.1) was determined by .sup.1H-NMR at 293 K and 323 K.

(24) TABLE-US-00001 complex conc., % of B, % of B, entry complex (M) 293 K 323 K 1 5e 1 mM 9 24 2 5f 1 mM 30 63 3 5f 0.5 mM 46 83 4 5f 6 mM 25 50 5 5g 1 mM 80 95

EXAMPLE 5

(25) Preparation of Ruthenium Complex 5a

(26) ##STR00009##

(27) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 4 (100 mg, 0.132 mmol), potassium 2,4,6-triphenylbenzenethiolate (56 mg, 0.155 mmol) 2a, and tetrahydrofuran (5 mL). After the addition of the solvent the color of the suspension changed rapidly from green to reddish-brown. The mixture was stirred at room temperature for three hours, during this time the color of the solution changes again from reddish-brown to dark-brown-greenish (the green color is due to the formation of a decomposition product). The solvent was removed under reduced pressure. The residual was extracted several times with pentane (in total about 20 mL) and the pentane solution was filtered through a short pad of celite. The solvent was again removed under vacuum and the dark-green residual was dissolved in 3 mL of toluene. Then 1 g of activated basic alumina and a stirring bar were added to the vial containing the toluene solution and the mixture was stirred for about 30 minutes. During this time the basic alumina becomes yellow-brownish and the toluene solution becomes dark green. The solution was removed with a Pasteur pipette and the impregnated basic alumina was washed repeatedly with 1 mL of toluene (7-8 times), until the color of the toluene extract was pale yellow. The resulting impregnated basic alumina, purified from the green colored decomposition product, was extracted two times with 100 L of a solution of pyridine in toluene (10% vol) followed by 2 mL of toluene. The solvent was removed under vacuum, the residual dissolved in a minimum amount of toluene, and then 5 mL of pentane was slowly added until the solution became slightly cloudy. The vial was placer in the freezer (32 C.) for a couple of days. The red-brown solid was isolated, washed three times with pentane and dried under vacuum to give 17 mg (12%) of 5a.C.sub.5H.sub.12. .sup.1H NMR (600.17 MHz, C.sub.6D.sub.6, 283 K): =17.15 (br s, 0.97H), 16.90 (s, 0.03H), 9.17-8.92 (br, 1H), 7.88-7.22 (br m, 10H), 7.12-6.96 (m, 8H), 6.96-6.24 (br m, 8H), 6.24-5.06 (br, 2H), 2.88 (s, 0.09H), 2.80 (s, 2.91H), 2.45-2.26 (br m, 12H), 1.59 (s, 3H), 1.44 (s, 3H), 1.35 (s, 3H). .sup.13C{.sup.1H} NMR (150.91 MHz, C.sub.6D.sub.6, 283 K): 276.34 (br), 272.39 (br), 179.41 (br), 164.87 (br), 157.77 (br), 153.32, 151.19, 150.08, 144.89, 144.50, 143.72, 141.12, 138.88, 138.38, 137.77, 137.48, 136.88 (br), 136.31, 136.19 (br), 135.08, 134.34, 133.84, 133.13 (br), 130.95, 130.65, 130.01, 129.23, 128.84, 128.35, 127.57, 127.48, 127.23, 126.77, 126.62, 125.94, 125.73, 122.24, 21.46, 21.31, 21.14, 20.55, 19.95, 19.63, 19.21, 17.96, 9.69, 9.20, 9.02. Elemental analysis, calculated for C.sub.57H.sub.54ClN.sub.3RuS.sub.2: C, 69.74; H, 5.54; N, 4.28; found: C, 69.51; H, 5.18; N, 3.99.

EXAMPLE 6

(28) Preparation of Ruthenium Complex 7a

(29) ##STR00010##

(30) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 6 (100 mg, 0.138 mmol), potassium 2,4,6-triphenylbenzenethiolate (67 mg, 0.178 mmol) 2a, and tetrahydrofuran (5 mL). After the addition of the solvent the color of the suspension changed rapidly from green to reddish-brown. The mixture was stirred at room temperature for three hours, during this time the color of the solution changes from reddish-brown to dark-green (the green color is due to the formation of a decomposition product). The solvent was removed under reduced pressure. The residual was extracted several times with pentane (in total about 20 mL) and the pentane solution was filtered through a short pad of celite. The solvent was again removed under vacuum and the dark-green residual was dissolved in 3 mL of toluene. Then 1 g of activated basic alumina and a stirring bar were added to the vial containing the toluene solution and the mixture was stirred for about 30 minutes. During this time the basic alumina becomes yellow-green and the toluene solution becomes less intensely colored. The solution was removed with a Pasteur pipette and the basic alumina was washed repeatedly with 1 mL of toluene (7-8 times) until the color of the alumina was yellow-brown and the color of the toluene extract was pale yellow. The resulting impregnated alumina, was extracted two times with 100 L of a solution of pyridine in toluene (10% vol) followed by 2 mL of toluene. The solvent was removed under vacuum, the residual dissolved in a minimum amount of toluene and pentane (about 5 mL) was slowly added until the solution became slightly cloudy. The vial was placed in the freezer (32 C.) for a couple of days. The red-brown microcrystals were isolated, washed three times with pentane and dried under vacuum to give 38 mg (27%) of 7b.C.sub.5H.sub.12. .sup.1H NMR (600.17 MHz, C.sub.6D.sub.6, 283 K): =17.90 (s, 0.98 H), 16.06 (s, 0.02 H), 9.75-8.04 (br, 1H), 8.07-7.28 (br, 9H), 7.28-7.03 (m, 5H), 7.03-6.98 (m, 4H), 6.98-6.73 (br, 6H), 6.72-6.45 (br, 2H), 6.45-6.30 (m, 2H), 6.26-5.33 (br, 2H), 3.31 (br, 1H), 3.14 (br m, 2H), 3.00 (br, 1H), 2.94 (br s, 3H), 2.62 (br s, 3H), 2.52 (br s, 3H), 2.35 (br s, 3H), 2.29 (br s, 3H), 1.65 (br s, 3H). .sup.13C{.sup.1H} NMR (150.91 MHz, C.sub.6D.sub.6, 283 K): 299.49, 214.20, 152.86 (br), 150.65, 150.25, 149.56, 144.94, 144.32, 142.96, 141.04, 139.36, 139.09, 137.47, 137.28, 136.85, 136.42, 136.20, 134.19, 131.54, 130.96, 130.42, 130.33, 129.93, 129.88, 129.45, 129.03, 128.83, 128.35, 127.98, 127.80, 127.54, 126.82, 126.73, 126.49, 125.99, 122.46, 51.73, 50.63, 24.34, 21.41, 21.27, 20.72, 19.61, 17.86. Elemental analysis, calculated for C.sub.57H.sub.54ClN.sub.3RuS: C, 72.09; H, 5.73; N, 4.42; found: C, 72.45; H, 5.85; N, 4.15. HRMS (DART): calculated for C.sub.52H.sub.50.sup.35ClN.sub.2.sup.102RuS [Mpy+H].sup.+: m/z=871.2427, found: m/z=871.2440.

EXAMPLE 7

(31) Preparation of Ruthenium Complex 7f

(32) ##STR00011##

(33) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 6 (80 mg, 0.112 mmol), potassium 2,4,6-tris(3,5-dimethylphenyl)benzenethiolate (58 mg, 0.125 mmol) 2f, and tetrahydrafuran (4 mL). After the addition of the solvent the color of the suspension changed rapidly from green to reddish-brown. The mixture was stirred at room temperature for two hours. The solvent was removed under reduced pressure. The residual was dissolved in a minimum amount of toluene (about 1 mL), then 3 mL of pentane were added and the resulting dark-brown mixture was rapidly filtered through celite. The filtrate was placed in the freezer (32 C.) for a couple of days. The red-brown micro-crystalline solid was isolated, washed three times with pentane and dried in the glove box to give 70 mg (56%) of 7f. C.sub.5H.sub.12. .sup.1H NMR (600.17 MHz, C.sub.6D.sub.6): =18.54 (s, 0.91H), 17.04 (s, 0.09H), 8.66-5.56 (m, 23H), 3.47-3.35 (m, 0.91H), 3.27-3.10 (m, 2H), 3.10-3.00 (m, 1.09H), 2.98 (s, 2.73), 2.69 (s, 2.73H), 2.63-2.25 (m, 20.59H), 2.23 (s, 0.54H), 2.15 (0.54H), 2.07 (s, 0.54H), 2.02 (s, 5.5H), 1.63 (s, 2.73H). .sup.13C{.sup.1H} NMR (150.91 MHz, C.sub.6D.sub.6): =302.05, 301.63, 287.22, 215.14, 207.65, 153.43 (br), 151.87, 151.65, 151.35, 145.55, 145.01, 143.73, 141.13, 141.09, 139.83, 139.13, 138.63, 138.07, 137.89, 137.45, 137.19, 136.99, 136.63 (br), 136.40, 136.12, 135.90, 135.77, 134.31, 131.83, 131.40 (br), 130.40, 129.79, 129.58, 129.24, 129.09, 128.69, 128.35, 127.46, 126.65, 124.99, 124.66, 122.64, 51.78, 51.29, 50.44, 22.22, 21.86, 21.46, 21.41, 21.36, 21.20, 20.57, 19.54, 19.51, 19.07, 17.76. Elemental analysis, calculated for C.sub.63H.sub.66ClN.sub.3RuS: C, 73.19; H, 6.43; N, 4.06; found: C, 73.56; H, 6.49; N, 3.80. HRMS (DART): calculated for C.sub.58H.sub.61.sup.35ClN.sub.2.sup.101RuS [Mpy].sup.+: m/z=953.3300, found: m/z=953.3293.

EXAMPLE 8

(34) Preparation of Ruthenium Complex 9a

(35) ##STR00012##

(36) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 8 (100 mg, 0,121 mmol), potassium 2,4,6-triphenylbenzenethiolate (47.6 mg, 0,126 mmol) 2a, and tetrahydrofuran (5 mL). The mixture was stirred at room temperature for 2 hours, and then it was filtered through a short pad of celite. The filtrate was concentrated under reduced pressure to about 2 mL. Then 3 mL of pentane was slowly added to the solution and the vial was placed overnight in a freezer at 32 C. The dark red microcrystals (92 mg, yield 72%) were collected by decantation, washed three times with pentane and dried in the glove box to give 92 mg (72%) of 9a. .sup.1H NMR (600.17 MHz, CDCl.sub.3): =8.62 (br s, 0.32H), 8.48 (br d, .sup.3J.sub.HH=5.2, 0.68H), 8.13 (br d, .sup.3J.sub.HH=7.2, 1.36H), 7.88 (br d, .sup.4J.sub.HH=1.4, 0.32H), 7.79-7.27 (m, 15.2H), 7.24-6.73 (m, 9.90H), 6.54 (br d, .sup.3J.sub.HH=5.2, 0.64H), 6.47 (br d, .sup.3J.sub.HH=5.9, 0.32H), 6.45-6.37 (m, 1.36H), 6.36-6.23 (m, 1.62H), 6.17 (s, 1.36H), 6.06-5.89 (m, 2.0H), 5.81 (t, .sup.3J.sub.HH=5.9, 0.32H), 5.76 (d, .sup.3J.sub.HH=8.0, 0.32H), 6.45-6.37 (m, 1.36H), 6.36-6.23 (m, 1.62H), 6.17 (s, 1.36H), 6.05-5.88 (m, 2.0H), 5.81 (t, .sup.3J.sub.HH=5.9, 0.32H), 5.76 (d, .sup.3J.sub.HH=8.0, 0.32H), 5.29-5.20 (m, 1.0H, 5.18 (t, .sup.3J.sub.HH=5.9, 0.32H), 5.10 (s, 0.32H), 4.15 (t, .sup.3J.sub.HH=5.9, 0.32H), 2.38 (s, 2.04H), 2.33 (s, 0.96H), 2.31 (s, 2.04H), 2.23 (s, 0.96H), 2.21 (s, 2.04H), 2.16 (s, 0.96H), 2.08 (s, 0.96H), 2.08 (s, 0.96H), 2.06 (s, 0.96H), 1.66 (s, 2.04H), 1.63 (s, 0.96H), 1.58 (s, 2.04H), 1.02 (s, 2.04H). .sup.13C{.sup.1H} NMR (150.91 MHz, CDCl.sub.3): =270.77, 183.31, 180.30, 159.11, 154.03, 150.03, 149.76, 147.98, 147.61, 146.70, 145.50, 145.15, 142.85, 142.82, 142.70, 141.54, 141.13, 140.49, 140.10, 139.64, 139.59, 139.15, 139.05, 138.77, 138.58, 138.04, 137.34, 137.25, 137.09, 137.04, 136.79, 136.67, 136.00, 135.96, 135.90, 135.47, 134.62, 134.55, 134.09, 133.76, 133.69, 132.97, 131.96, 130.75, 130.34, 130.01, 129.88, 129.73, 129.51, 129.44, 129.27, 129.22, 129.14, 129.09, 128.68, 128.44, 128.36, 128.23, 128.06, 127.87, 127.72, 127.65, 127.60, 127.45, 127.28, 127.14, 126.92, 126.82, 126.68, 126.55, 126.47, 126.35, 126.28, 125.88, 125.77, 125.58, 125.35, 125.31, 125.11, 124.38, 124.33, 123.98, 123.85, 123.41, 122.48, 121.56, 117.38, 99.74, 93.89, 90.90, 89.47, 87.80, 78.93, 63.76, 21.21, 21.14, 20.96, 20.90, 20.80, 20.16, 20.02, 19.85, 19.57, 18.60, 18.42, 18.23.

EXAMPLE 9

(37) Preparation of Ruthenium Complex 11f

(38) ##STR00013##

(39) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 10 (50 mg, 0.057 mmol), potassium 2,4,6-tris(3,5-dimethylphenyl)benzenethiolate (26 mg, 0.057 mmol) 2f, and toluene (4 mL). After the addition of the solvent the color of the suspension changed rapidly from green to reddish-brown. The mixture was stirred at room temperature for two hours and then filtered through celite. The solvent was removed under reduced pressure to give 58 mg (92%) of 11f. .sup.1H NMR (500.13 MHz, C.sub.6D.sub.6): =18.41 (s, 0.58H), 17.00 (s, 0.42H), 8.62 (br s, 0.84H), 8.19 (br s, 0.84H), 7.61-7.54 (br m, 0.84H), 7.45-7.26 (br m, 0.84H), 7.29-7.24 (br m, 1H), 7.20-7.18 (br, 1H), 7.07-7.04 (br m, 0.84H), 6.98-6.63 (br m, 15.82H), 6.37 (br s, 0.84H), 6.26 (br s, 0.58H), 5.61 (br s, 0.58H), 3.61-3.00 (br m, 4H), 2.93 (br s, 1.74H), 2.66 (br s, 1.74H), 2.53-2.35 (br m, 14.22H), 2.30 (br s, 1.26H), 2.29 (br s, 1.74H), 2.25-2.21 (br s, 2.52H), 2.17 (s, 1.26H), 2.15 (s, 1.26H), 2.11 (s, 3.78H), 2.08 (br s, 1.26H), 2.00 (br s, 3.48H), 1.60 (br s, 1.74H). .sup.13C{.sup.1H} NMR (150.91 MHz, C.sub.6D.sub.6): =302.12, 214.30, 153.12, 152.02, 151.54, 151.37, 149.70, 148.06, 145.60, 144.82, 142.91, 142.27, 142.06, 140.98, 140.04, 139.03, 138.08, 137.58, 137.36, 137.15, 136.65, 135.36, 131.65, 130.40, 129.63, 129.33, 129.27, 129.23, 129.17, 128.77, 128.35, 127.66, 125.16, 124.72, 123.56, 118.40, 51.83, 51.43, 50.35, 22.13, 21.54, 21.43, 21.37, 21.34, 20.51, 19.56, 19.03, 17.72. HRMS (ESI.sup.+): calculated for C.sub.58H.sub.62N.sub.2.sup.102RuS [M3Br-PyCl+H].sup.+: m/z=920.36772, found: m/z=920.36851.

EXAMPLE 10

(40) Preparation of Ruthenium Complex 13f

(41) ##STR00014##

(42) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 12 (50 mg, 0.076 mmol), potassium 2,4,6-tris(3,5-dimethylphenyl)benzenethiolate (35 mg, 0.076 mmol) 2f, and toluene (2 mL). The mixture was stirred for 10 hours at room temperature. The mixture was filtered through a pad of celite. The solvent was reduced by half under vacuum and then pentane (about 5 mL) was slowly added until the solution became slightly cloudy. The mixture was placed in the freezer (32 C.) for a couple of days. The brown microcrystals were isolated, washed three times with pentane and dried under vacuum to give 18 mg (25%) of 13f. .sup.1H NMR (600.17 MHz, C.sub.6D.sub.6): =17.46 (s, 1H), 7.92 (br d, .sup.3J.sub.HH=7.7 Hz, 2H), 7.75 (br s, 3H), 7.28 (br tt, .sup.3J.sub.HH=7.4 Hz, .sup.4J.sub.HH=1.1 Hz, 1H), 7.22 (s, 2H), 7.07 (br s, 1H), 7.01 (br dd, .sup.3J.sub.HH=8.1 Hz, .sup.4J.sub.HH=7.4 Hz, 2H), 6.96 (br s, 1H), 6.93 (br s, 1H), 6.83-6.02 (m, 7H), 3.09-2.90 (m, 4H), 2.51-2.34 (m, 12H), 2.31-215 (m, 9H), 2.08 (s, 6H), 2.04 (s, 6H), 1.54 (br s, 3H). .sup.13C{.sup.1H} NMR (150.91 MHz, C.sub.6D.sub.6): 302.11, 210.36, 151.98, 149.54, 147.96, 145.98, 144.14, 143.68, 141.16, 140.66, 138.67, 138.49, 138.12, 138.07, 136.83, 135.75, 134.91, 131.83, 131.07, 129.97, 129.93, 129.64, 128.90, 128.59, 128.46, 128.35, 124.91, 124.74, 114.06, 50.84, 22.32, 21.77, 21.40, 21.20, 21.02, 19.36, 18.76. HRMS (ESI.sup.+): calculated for C.sub.58H.sub.62N.sub.2.sup.102RuS [MNCO+H].sup.+: m/z=920.36772, found: m/z=920.36701.

EXAMPLE 11

(43) Preparation of Ruthenium Complex 14g

(44) ##STR00015##

(45) In a glovebox, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with complex 5g (22 mg, 0.017 mmol) and pentane (5 mL). The mixture was stirred for a few minutes in such a way to achieve a dark-brown solution. Then 250 mg of activated basic alumina was added to the vial and the mixture was stirred for about 30 minutes. During this time the basic alumina becomes brown and the pentane solution becomes pale yellow-brown in color. The solution was removed with a Pasteur pipette and the basic alumina was washed five times with about 5 mL of pentane by following this procedure: The impregnated alumina and pentane were stirred for a few minutes until the pentane extract became slightly colored of pale yellow-brown, the stirring was stopped and the mixture was decanted. Then the pentane solution was removed with a Pasteur pipette.

(46) After this treatment, the brown colored alumina was extracted three times with about 2 mL of toluene. The dark-brown solution was filtered through a glass-fiber paper and solvent was removed under vacuum to give 12 mg (58%) of 14g. .sup.1H NMR (600.17 MHz, C.sub.6D.sub.6): =17.35 (s, 1H), 8.14 (br s, 2H), 7.89 (br s, 1H), 7.69 (br dt, .sup.3J.sub.HH=4.9 Hz, .sup.4J.sub.HH=1.1 Hz, 1H), 7.60 (br s, 1H), 7.57 (br d, .sup.4J.sub.HH=1.8 Hz, 2H), 7.52 (br s, 1H), 7.55 (br m, 1H), 7.44 (br t, .sup.4J.sub.HH=1.8 Hz, 1H), 7.02 (br s, 1H), 6.91 (br s, 1H), 6.80 (br s, 1H), 6.69 (s, 2H), 6.66 (br dd, .sup.3J.sub.HH=4.9 Hz, .sup.3J.sub.HH=4.9 Hz, .sup.3J.sub.1-iii=4.9 Hz, 1H), 6.63 (br, 2H), 2.34 (s, 6H), 2.15 (s, 6H), 2.07 (s br, 6H), 1.50 (s, 27H), 1.28 (s, 6H), 1.25 (s, 18H), 0.97 (br, 1H), 0.90 (br s, 9H). .sup.13C{.sup.1H} NMR (150.91 MHz, C.sub.6D.sub.6): 276.97, 174.63, 166.23, 157.00, 156.64, 151.09, 150.83, 149.71, 146.60, 143.89, 141.60, 138.78, 138.40, 138.24, 138.13, 136.93, 133.69, 133.39, 130.64, 129.79, 129.45, 128.35, 127.61, 127.27, 125.54, 124.09, 121.90, 120.53, 120.32, 111.75, 35.54, 35.19, 34.94, 32.01, 31.61, 30.20, 21.23, 20.14, 19.62, 9.05.

EXAMPLE 12

(47) Homocoupling of Neat Allylbenzene

(48) ##STR00016##

(49) In a glove box, a 4 mL vial equipped with a magnetic stirring bar was charged with 59 mg (0.50 mmol) of allylbenzene and the catalyst (0.005 mmol, 1 mol %). The reaction mixture was stirred at room temperature (22 C.) for five minutes (open atmosphere). The reaction was quenched by filtration through silica gel using hexane as eluent. Determination of conversions, yields, and Z-selectivities were done according to literature procedures. (20, 28)

(50) TABLE-US-00002 % entry cat. 21/22.sup.a Yield of 21.sup.b Z-21.sup.a 1 5e 48 64 66 2 5f >100 73 80 3 5g 9 28 86 4 5a 63 69 63 5 7a 15 41 81 6 7f 51 33 86 7 9a >100 8 83 8 11f >100 50 75 10 13f 6 67 68 11 14g >100 31 79 12 D1-4d.sup.c 0.2 2 83 13 D2-4a.sup.c 0.6 3 87 .sup.aDetermined by .sup.1H NMR. .sup.bIsolated yield. .sup.cSee FIG. 2 for the Lewis structure and literature references.

EXAMPLE 13

(51) Homocoupling of Neat Terminal Olefin with Catalyst 5f

(52) In a glove box, a 4 mL vial equipped with a magnetic stirring bar and a screw cap was charged with 0.50 mmol of substrate, 2 mg of hexamethylbenzene (internal standard) and the catalyst (0.005 mmol, 1 mol %). The vial was closed and the reaction mixture was stirred at room temperature (22 C.) for five minutes. The reaction was quenched with an excess of ethyl vinyl ether. Determination of conversions, yields, and Z-selectivities were done according to literature procedures. (20, 28)

(53) TABLE-US-00003 % entry substrate % conv..sup.a % yield.sup.a Z.sup.a 1 1-octene 68 68 79 2 allylacetate 46 46 80 3 4-phenyl-1-butene 76 75 79 4 allyl boronic acid pinacol ester 61 53 94 5 N-allylanyline 14 14 75 6 2-allyloxyethanol 2 2 78 .sup.aDetermined by .sup.1H NMR.

EXAMPLE 14

(54) Homocoupling of Terminal Olefins in Toluene Solution (1 M) at Room Temperature

(55) ##STR00017##

(56) Reactions under ambient pressure: In a glove box, a 4 mL vial equipped with a magnetic stirring bar and a screw cap was charged with the substrate (0.1 mmol) and 2 mg of hexamethylbenzene (internal standard). Then a solution of the catalyst (510.sup.3 mmol, 5 mol %) dissolved in the right amount of toluene to achieve the final concentration of 1 M in substrate, was added to the vial containing the substrate and the internal standard. The vial was closed and the reaction mixture was stirred at room temperature (22 C.). Samples (about 10 L) of the reaction mixture were withdrawn at regular time intervals, and quenched with an excess of ethyl vinyl ether. Determination of conversions, yields, and Z-selectivities were carried out by comparing the integrals of the peaks due to the olefinic protons of substrates and products, identified by comparison with literature data, (20, 37-41) with that of the internal standard.

(57) Reactions under static vacuum: In a glove box, a 50 mL Schlenk flask equipped with a Young's tap and a magnetic stirring bar was charged with the substrate (0.1 mmol) and 2 mg of hexamethylbenzene (internal standard). Then a solution of the catalyst (510.sup.3 mmol, 5 mol %) dissolved in the right amount of toluene to achieve the final concentration of 1 M in substrate, was added to the flask. The flask was closed, exported outside the glovebox, and the mixture was immediately frozen in liquid nitrogen. The flask was then evacuated to about 10.sup.2 mbar and closed, allowed to heat to room temperature and stirred. Samples (about 10 L) of the reaction mixture were withdrawn at regular time intervals, and quenched with an excess of ethyl vinyl ether. In order to take a sample, the progress of the reaction was stopped by cooling the reaction mixture with liquid nitrogen, and the flask was backfilled with argon. Then the static vacuum was restored by using the same procedure described above. Determination of conversions, yields, and Z-selectivities were carried out by comparing the integrals of the peaks due to the olefinic protons of substrates and products, identified by comparison with literature data, (20, 37-41) with that of the internal standard.

(58) TABLE-US-00004 pressure, time, % entry substrate cat. mbar minutes % conv.sup.a yield.sup.a Z.sup.a 1 10-undecenoic acid 5f 1 5 50 50 66 10 56 56 57 2 10-undecenoic acid 5f 1 .Math. 10.sup.2 5 59 56 67 3 10-undecenoic acid 7f 1 .Math. 10.sup.2 5 34 28 45 4 10-undecenoic acid 5g 1 .Math. 10.sup.2 5 33 28 35 5 10-undecenoic acid 13f 1 .Math. 10.sup.2 5 74 15 24 6 10-undecenoic acid D2-4a.sup.b 1 5 4 <1 n.d 7 10-undecenoic acid D2-4a.sup.b 1 .Math. 10.sup.2 5 10 <1 n.d. 8 4-pentenoic acid 5f 1 5 43 30 69 10 50 32 54 9 4-pentenoic acid 5f 1 .Math. 10.sup.2 5 35 35 79 25 44 42 70 60 50 42 54 10 4-pentenoic acid GII.sup.c 1 .Math. 10.sup.2 25 17 17 11 60 46 45 8 11 2-Allyloxyethanol 5f 1 5 50 50 52 12 2-Allyloxyethanol 7f 1 5 48 35 57 13 2-Allyloxyethanol D2-4a.sup.b 1 5 0 0 .sup.aDetermined by .sup.1H NMR (Internal Standard = hexamethylbenzene). .sup.bSee FIG. 2 for the Lewis structure and literature references. .sup.cGII = Grubbs second generation catalyst.

EXAMPLE 15

(59) Ring Closing Metathesis of Diene 22

(60) ##STR00018##

(61) Reactions under ambient pressure: In a glove box, a 25 mL vial, equipped with a magnetic stirring bar and a screw cap, was charged with 3 mg (0.0126 mmol) of diene 22, 1.5 mg of hexamethylbenzene (internal standard) and about 90% of the total amount of toluene. In a different vial 5f was dissolved with the remaining amount of toluene and the resulting solution was transferred to the first vial. The vial was closed and the mixture was stirred at room temperature (22 C.). Samples (0.5 mL) of the reaction mixture were withdrawn at regular time intervals, and quenched with an excess of ethyl vinyl ether, the solvent was removed by vacuum, and the residual was analyzed by .sup.1H NMR (600 MHz and 850 MHz). Determination of conversions, yields, and Z-selectivities were obtained from the analysis of 600 and 850 MHz .sup.1H NMR spectra. (24, 42)

(62) TABLE-US-00005 cat. sub. load, conc. T time, % % entry cat. mol % (mM) ( C.) hours conv..sup.a yield.sup.a Z.sup.a 1 5f 10 3 22 1 70 19 74 2 75 38 70 4 81 62 53 9 88 71 42 22 92 77 30 2 5f 10 1 22 2 48 41 73 8 71 57 63 22 81 72 48 3 5f 20 1 22 2 59 52 68 4 69 62 58 8 79 72 47 22 95 88 41 4.sup.b 5f 10 1 100 0.33 62 49 73 1 87 64 64 1.5 91 69 63 5 7f 10 3 22 1 51 17 80 6 9a 10 3 22 1 64 33 58 22 86 53 57 7 D1-4d.sup.c 10 3 22 1 86 2 68 8 D2-4a.sup.c 10 3 22 1 81 0 9 GII.sup.d 10 3 22 1 85 67 10 .sup.aDetermined by analysis of 600 and 850 MHz .sup.1H NMR spectra of unpurified mixtures (internal standard hexamethylbenzene). .sup.bThe reaction was carried out in a 300 mL Schlenk flask equipped with a Young's tap. The reaction mixture was prepared inside a glove box, the flask was closed, exported in a fume hood and connected to a Schlenk line, and then heated at 100 C. in a preheated oil bath and stirred. .sup.cSee FIG. 2 for the Lewis structure and literature references. .sup.dGII = Grubbs second generation catalyst.

(63) Reactions at 60 C. and Under Static Vacuum (10.sup.2 Mbar): In a glove box, a 50 mL Schlenk flask equipped with a Young's tap and a magnetic stirring bar was charged with 3 mg (0.0126 mmol) of diene 22, 1.5 mg of hexamethylbenzene (internal standard) and about 90% of the total amount of toluene. In a different vial the catalyst (0.00126 mmol) was dissolved with the remaining amount of toluene and the resulting solution was transferred to the flask. The flask was closed, exported outside the glovebox, and the mixture was immediately frozen in liquid nitrogen. The flask was then evacuated to about 10.sup.2 mbar and closed, heated first by immersion in a tepid water bath and then heated at 60 C. in a preheated oil bath or immersed in an ice-water bath and stirred. Samples (0.5 mL) of the reaction mixture were withdrawn at regular time intervals, and quenched with an excess of ethyl vinyl ether, the solvent was removed by vacuum, and the residual was analyzed by .sup.1H NMR (600 MHz and 850 MHz). Determination of conversions, yields, and Z-selectivities were obtained from the analysis of 600 and 850 MHz .sup.1H NMR spectra. (24, 42)

(64) TABLE-US-00006 cat. sub. load, conc. T time, % yield.sup.a % entry cat. mol % (mM) ( C.) hours conv..sup.a (isol).sup.b Z.sup.a 1.sup.b 5f 10 3 60 2 94 71 54 (56) .sup.(57).sup.c 2 5g 10 3 60 2 75 10 60 3 7f 10 3 60 2 65 23 72 4 D1-4d.sup.d 10 3 60 2 89 <1 n.d. 5 D2-4a.sup.d 10 3 60 2 77 0 6 5f 5 10 0 2 25 8 72 .sup.aDetermined by analysis of 600 and 850 MHz .sup.1H NMR spectra of unpurified mixtures (internal standard hexamethylbenzene). .sup.bThe reaction was carried out in a 300 mL Schlenk flask and on a larger scale (0.20 mmol of diene 22). The product was isolated by column chromatography on silica gel using pentane/diethyl ether (92:8) as eluent. .sup.cDetermined by analysis of 600 MHz .sup.1H NMR spectrum of the isolated product. .sup.dSee FIG. 2 for the Lewis structure and literature references.

EXAMPLE 16

(65) Ring Closing Metathesis of Diene 24

(66) ##STR00019##

(67) In a glove box, a 300 mL Schlenk flask, equipped with a magnetic stirring bar, was charged with the diene 24 (0.126 mmol), then 120 mL (i.e. about 95 of the total amount of solvent to prepare a 1 mM solution) was added to the flask. In a vial 5f (0.0126 mmol) was dissolved in 6 ml (i.e. the remaining amount of solvent to prepare a 1 mM solution) of toluene and the resulting solution was transferred to the Schlenk flask. The flask was closed, exported outside the glovebox, and the mixture was immediately frozen in liquid nitrogen. The flask was then evacuated to about 10.sup.2 mbar and closed, heated first by immersion in a tepid water bath and then heated at 100 C. in a preheated oil bath and stirred for one hour. The reaction was quenched with an excess of ethyl vinyl ether, the solvent was removed by vacuum, and the product 25 was isolated by column chromatography on silica gel using pentane/diethyl ether (85:15) as eluent. Determination of Z-selectivities were obtained from the analysis of 600 .sup.1H NMR spectra.

(68) TABLE-US-00007 cat. sub. load, conc. T time, % % entry cat. mol % (mM) ( C.) hours conv..sup.a yield.sup.b Z.sup.c 1 5f 10 1 100 1 94 56 57 .sup.aDetermined by analysis of 600 MHz .sup.1H NMR spectrum of unpurified mixture. .sup.bIsolated yield. .sup.cDetermined by analysis of 600 MHz .sup.1H NMR spectrum of the isolated product.

REFERENCES

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