ethenylcyclohexane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 100 ml of dehydrated pure n-heptane was added 1.95 g of triethyl aluminium, 675 mg of ethyl p-anisate and 6.0 g of titanium compound catalyst prepared according to Example 1 of Published Unexamined Japanese Patent Application No. 57-59916 in this order, and the temperature of the mixture was elevated to 50° C. Subsequently, 50 g of vinylcyclohexane was added to the mixture and polymerization of vinylcyclohexane wa continued for 15 minutes. The resulting polymer slurry was washed with 200 ml of n-heptane four times to remove unused vinylcyclohexane, triethylaluminium as a cocatalyst and ethyl p-anisate. Then, n-heptane was removed from the washed acitve slurry by distillation under reduced pressure to obtain 7.8 g of powder of polyvinylcyclohexane containing acitve catalyst. The amount of polyvinylcyclohexane polymerized is 0.30 g per g of the charged titanium compound catalyst In a stainless steel autocave (inner volume: 5l) was performed polymerization of propylene using 1.06 g of the above-described vinylcyclohexane polymerization catalyst, 0.75 g of triethyl aluminium, 0.237 g of methyl p-toluylate and 1,500 ml of n-heptane under the conditions of a pressure of 6 kg/cm2 guage and a temperature of 70° C. and a hydrogen concentration of 1.5% by volume for 40 minute. After completion of the polymerization, 50 ml of n-butanol was added to stop the polymerization and the resulting polymer slurry was taken out followed by the separation of polymer powder and solvent by filtration. After washing the polymer powder with 500 ml of 1N hydrochloric acid, further washing was performed with methanol until the washings became neutral. containing acitve catalyst The amount of polyvinylcyclohexane polymerized was added the polymerization the resulting polymer slurry was taken out followed by the separation of polymer powder and solvent by filtration After washing the polymer powder with 500 ml of 1N hydrochloric acid further washing

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the general procedure, vinylcyclohexane (20.0 mg, 0.182 mmol) was treated with p-methoxyphenyl vinyl ether (55.0 mg, 0.363 mmol) and 5 mol % of in situ-generated complex 1a (91.0 μL, 0.10 M, 9.08 μmol; final substrate concentration=2.0 M) and allowed to stir for 24 h. The unpurified product is >98% Z (as determined by 400 MHz 1H NMR analysis). Excess p-methoxyphenyl vinyl ether was removed by vacuum distillation (1.0 torr, 80° C.). The resulting oil was purified by neutral alumina chromatography (50:1 hexanes:Et2O) to afford 10d (31.8 mg, 0.137 mmol, 75.0% yield, >98% Z isomer) as a colorless oil. IR (neat): 2925 (m), 2850 (m), 1664 (w), 1505 (s), 1465 (w), 1447 (w), 1392 (w), 1293 (w), 1244 (m), 1224 (s), 1180 (w), 1102 (w), 1040 (m); 1H NMR (400 MHz, CDCl3): δ 6.95-6:91 (2H, m), 6.86-6.82 (2H, m), 6.17 (1H, dd, J=6.4, 1.2 Hz), 4.63 (1H, d, J=9.2, 6.0 Hz), 3.78 Hz (3H, s), 2.65-2.54 (1H, m), 1.78-1.60 (5H, m), 1.39-1.06 (5H, m); 13C NMR (100 MHz, CDCl3): δ 155.2, 151.9, 139.8, 118.6, 117.5, 114.8, 55.9, 33.6, 33.5, 26.3, 26.1; HRMS (ESI+) [M+H]+ calcd for C15H21O2: 233.1542, found: 233.1542. Excess p-methoxyphenyl vinyl ether was removed by vacuum distillation (1.0 torr, 80° C.) The resulting oil was purified by neutral alumina chromatography (50:1 hexanes:Et2O)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the general procedure, vinylcyclohexane (20.0 mg, 0.182 mmol) was treated with p-methoxyphenyl vinyl ether (55.0 mg, 0.363 mmol) and 5 mol % of in situ-generated complex 1a (91.0 μL, 0.10 M, 9.08 μmol; final substrate concentration=2.0 M) and allowed to stir for 24 h. The unpurified product is >98% Z (as determined by 400 MHz 1H NMR analysis). Excess p-methoxyphenyl vinyl ether was removed by vacuum distillation (1.0 torr, 80° C.). The resulting oil was purified by neutral alumina chromatography (50:1 hexanes:Et2O) to afford 10d (31.8 mg, 0.137 mmol, 75.0% yield, >98% Z isomer) as a colorless oil. IR (neat): 2925 (m), 2850 (m), 1664 (w), 1505 (s), 1465 (w), 1447 (w), 1392 (w), 1293 (w), 1244 (m), 1224 (s), 1180 (w), 1102 (w), 1040 (m); 1H NMR (400 MHz, CDCl3): δ 6.95-6:91 (2H, m), 6.86-6.82 (2H, m), 6.17 (1H, dd, J=6.4, 1.2 Hz), 4.63 (1H, d, J=9.2, 6.0 Hz), 3.78 Hz (3H, s), 2.65-2.54 (1H, m), 1.78-1.60 (5H, m), 1.39-1.06 (5H, m); 13C NMR (100 MHz, CDCl3): δ 155.2, 151.9, 139.8, 118.6, 117.5, 114.8, 55.9, 33.6, 33.5, 26.3, 26.1; HRMS (ESI+) [M+H]+ calcd for C15H21O2: 233.1542, found: 233.1542. Excess p-methoxyphenyl vinyl ether was removed by vacuum distillation (1.0 torr, 80° C.) The resulting oil was purified by neutral alumina chromatography (50:1 hexanes:Et2O)

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Iodobenzyl alcohol (2.34 g) was dissolved in DMF (40 mL), added with vinylcyclohexane (1.32 g), triethylamine (1.81 mL), and bis(triphenylphosphine)palladium (II) chloride (700 mg), and stirred for 23 hours at 80° C. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the residues were purified by silica gel column chromatography (8 to 30% ethyl acetate/hexane) to obtain the title compound (672 mg) as a yellow solid. After cooling to room temperature the solvent was evaporated under reduced pressure the residues were purified by silica gel column chromatography (8 to 30% ethyl acetate/hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Subsequently, in a 3 l-volume SUS-made autoclave equipped with a stirrer whose atmosphere had been displaced with nitrogen were successively charged 1 l of dehydration-purified n-heptane, 8.5 mmol of an organoaluminum compound of formula (C2H5)2Al(OBu)0.3 Cl0.7, 0.85 mmol of methyl toluylate, and 3.44 g of the above-obtained solid catalyst containing the vinylcyclohexane polymer. To the mixture were fed 50 g of propylene and hydrogen at a partial pressure 1.5 atm. to effect polymerization at 60° C. for 4 hours. During the polymerization, propylene was fed so as to maintain the polymerization pressure at 6 kg/cm2G. The polymerization was terminated by addition of 50 ml of butanol, and the inner pressure was released, followed by allowing to stand at 60° C. for 1 hour. The polymerization mixture was taken out and filtered to obtain 233 g of a vinyl-cyclohexane-propylene block copolymer. The polymer had an Mw/Mn of 11.8, a CXS of 1.8%, and an [η] of 1.81 dl/g and contained 13400 ppm of the vinylcyclohexane polymer component. Subsequently, in a 3 l-volume SUS-made autoclave equipped with a stirrer whose atmosphere polymerization at 60° C. for 4 hours to maintain the polymerization pressure at 6 kg/cm2G The polymerization was terminated by addition of 50 ml of butanol filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Subsequently, 1 of dehydration-purified n-heptane, 8.5 mmol of an organoaluminum compound of formula (C2H5)2Al(OBu)0.3 Cl0.7 (wherein OBu represents a butoxy group), 0.85 mmol of methyl toluylate, and 0.640 g of the above-obtained solid catalyst containing the vinylcyclohexane polymer were successively charged in a 3 l-volume SUS-made autoclave equipped with a stirrer whose atmosphere had been displaced with argon. Then, 50 g of propylene and hydrogen at a partial pressure of 1.5 atm. were added thereto to continue the polymerization for an additional period of 6 hours at 60° C. During the reaction, propylene was fed so as to maintain the polymerization pressure at 6 kg/cm2G. The polymerization was terminated by addition of 50 ml of butanol, and the inner pressure was released. After allowing to stand at 60° C. for 1 hour, the polymerization mixture was taken out and filtered to obtain 187.5 g of a vinyl-cyclohexane-propylene block copolymer. The polymer had an Mw/Mn of 12.5, an [η] of 1.98 dl/g, and a CXS of 1.0% and contained 1890 ppm of the vinylcyclohexane polymer component. were successively charged in a 3 l-volume SUS-made autoclave equipped with a stirrer whose atmosphere the polymerization for an additional period of 6 hours at 60° C to maintain the polymerization pressure at 6 kg/cm2G The polymerization was terminated by addition of 50 ml of butanol filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Subsequently, 1 of dehydration-purified n-heptane, 8.5 mmol of an organoaluminum compound of formula (C2H5)2Al(OBu)0.3 Cl0.7 (wherein OBu represents a butoxy group), 0.85 mmol of methyl toluylate, and 0.640 g of the above-obtained solid catalyst containing the vinylcyclohexane polymer were successively charged in a 3 l-volume SUS-made autoclave equipped with a stirrer whose atmosphere had been displaced with argon. Then, 50 g of propylene and hydrogen at a partial pressure of 1.5 atm. were added thereto to continue the polymerization for an additional period of 6 hours at 60° C. During the reaction, propylene was fed so as to maintain the polymerization pressure at 6 kg/cm2G. The polymerization was terminated by addition of 50 ml of butanol, and the inner pressure was released. After allowing to stand at 60° C. for 1 hour, the polymerization mixture was taken out and filtered to obtain 187.5 g of a vinyl-cyclohexane-propylene block copolymer. The polymer had an Mw/Mn of 12.5, an [η] of 1.98 dl/g, and a CXS of 1.0% and contained 1890 ppm of the vinylcyclohexane polymer component. were successively charged in a 3 l-volume SUS-made autoclave equipped with a stirrer whose atmosphere the polymerization for an additional period of 6 hours at 60° C to maintain the polymerization pressure at 6 kg/cm2G The polymerization was terminated by addition of 50 ml of butanol filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a stainless steel autoclave (inner volume: 5 l) was performed polymerization of propylene using 1.06 g of the above-described vinylcyclohexane polymerization catalyst, 0.75 g of triethyl aluminium, 0.237 g of methyl p-toluylate and 1,500 ml of n-heptane under the conditions of a pressure of 6 kg/cm2 gauge and a temperature of 70° C. and a hydrogen concentration of 1.5% by volume for 40 minute. After completion of the polymerization, 50 ml of n-butanol was added to stop the polymerization and the resulting polymer slurry was taken out followed by the separation of polymer powder and solvent by filtration. After washing the polymer powder with 500 ml of 1N hydrochloric acid, further washing was performed with methanol until the washings became neutral. was added the polymerization the resulting polymer slurry was taken out followed by the separation of polymer powder and solvent by filtration After washing the polymer powder with 500 ml of 1N hydrochloric acid further washing

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a stainless steel autoclave (inner volume: 5 l) was performed polymerization of propylene using 1.06 g of the above-described vinylcyclohexane polymerization catalyst, 0.75 g of triethyl aluminium, 0.237 g of methyl p-toluylate and 1,500 ml of n-heptane under the conditions of a pressure of 6 kg/cm2 gauge and a temperature of 70° C. and a hydrogen concentration of 1.5% by volume for 40 minute. After completion of the polymerization, 50 ml of n-butanol was added to stop the polymerization and the resulting polymer slurry was taken out followed by the separation of polymer powder and solvent by filtration. After washing the polymer powder with 500 ml of 1N hydrochloric acid, further washing was performed with methanol until the washings became neutral. was added the polymerization the resulting polymer slurry was taken out followed by the separation of polymer powder and solvent by filtration After washing the polymer powder with 500 ml of 1N hydrochloric acid further washing

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The catalysts of the invention are effective and practical chiral catalysts for enantioselective metathesis. Examples of AROM/CM reactions catalyzed by chiral catalysts of the invention are shown in Table 1. As shown in Example 1, treatment of 19 with 5 equivalents of styrene in the presence of 10 mol % catalyst 9 in THF (50° C.) leads to the formation of 20a in 80% ee and 71% isolated yield (>98% trans). Ru-catalyzed AROM/CM is highly selective with aliphatic olefins. With aliphatic olefins such as 1-heptene and sterically bulky vinylcyclohexane (entries 2-3), 20b-c are obtained in >98% ee, >98% trans and 57-60% yield. isolated yield (>98% trans)