N-苄基-1-苯基乙胺

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: According to the general procedure, a solution of 1-phenyl-N-(1-phenylethylidene)methanamine (50 mg, 0.24 mmol) and rac-32 (7.5 mg, 0.0048 mmol, 2.0 mol %) in CH2Cl2 (3 mL) was pressurized with H2 to 62 bar and stirred for 72 h. Filtration of the reaction mixture and evaporation of the solvent gave 43 as a clear oil (45 mg, 88%). 1H NMR29 (300 MHz, CDCl3): δ 7.35-7.27 (m, 10H), 3.85 (q, 1H, J=6.6 Hz), 3.66 (ABq, 2H, J=13.2 Hz), 1.59 (bs, 1H), 1.39 (d, 3H, J=6.6 Hz); 13C NMR (75.5 MHz, CDCl3): δ 145.7, 140.8, 128.6, 128.5, 128.3, 127.0, 126.95, 126.8, 57.6, 51.8, 24.7. Filtration of the reaction mixture and evaporation of the solvent

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Benzyl-(1-phenylethyl)amine, conversion>99%, ee 82% (GC, sample derivatised by treatment with acetic anhydride pyridine, Chirasil DEX CB, 25 m×0.25 mm, injector/detector 200° C., helium 20 psi, 170° C. for 40 minutes then ramp at 15° C./min to 200° C., retention times 29.71 minutes and 30.73 minutes). then ramp at 15° C./min to 200° C., retention times 29.71 minutes and 30.73 minutes

反应条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a dry Schlenk tube under argon was placed (R,R)-Ethylene-1,2-bis(η5 -4,5,6,7-tetrahydroindenyl) titanium (R)-1,1'-binaphth-2,2'-diolate (25 mg, 0.042 mmol) and THF (4 mL). A solution of n-butyllithium (53 μL, 0.084 mmol, 1.6M in hexane) was added and the mixture was stirred for 10 minutes, at which time the color was a dark shade of brown. Phenylsilane (13 μL, 0.105 mmol) was then added and the mixture was stirred for another 10 minutes, the color changing to a darker shade of brown. Acetophenone N-benzyl imine (87 mg, 0.42 mmol) was then added and the reaction vessel was sealed and moved to a dry box. The reaction mixture was transferred to a Parr high pressure reactor, which was sealed and removed from the dry box. The reactor was charged with hydrogen to 1900 psi and heated to 65° C. After stirring for 48 hours the mixture was opened to air and concentrated. The residue was diluted with diethyl ether (20 mL) and extracted with 1N HCl (3×10 mL). The combined aqueous layers were basified with NaOH until strongly basic to pH paper and extracted with diethyl ether (4×25 mL). The organic layers were combined, dried over sodium sulfate and concentrated to produce 82-89% yield of N-benzyl-1-phenylethylamine. The enantiomeric excess (ee), as determined by HPLC analysis of the free amine using a Chiralcel OD column, was 89-92% in favor of the (R)enantiomer. In a dry Schlenk tube under argon was placed the mixture was stirred for another 10 minutes the reaction vessel was sealed moved to a dry box was sealed removed from the dry box The reactor was charged with hydrogen to 1900 psi After stirring for 48 hours the mixture concentrated The residue was diluted with diethyl ether (20 mL) extracted with 1N HCl (3×10 mL) extracted with diethyl ether (4×25 mL) dried over sodium sulfate concentrated

反应条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a dry Schlenk tube under argon was placed (R,R)-Ethylene-1,2-bis(η5 -4,5,6,7-tetrahydroindenyl) titanium (R)-1,1'-binaphth-2,2'-diolate (25 mg, 0.042 mmol) and THF (4 mL). A solution of n-butyllithium (53 μL, 0.084 mmol, 1.6M in hexane) was added and the mixture was stirred for 10 minutes, at which time the color was a dark shade of brown. Phenylsilane (13 μL, 0.105 mmol) was then added and the mixture was stirred for another 10 minutes, the color changing to a darker shade of brown. Acetophenone N-benzyl imine (87 mg, 0.42 mmol) was then added and the reaction vessel was sealed and moved to a dry box. The reaction mixture was transferred to a Parr high pressure reactor, which was sealed and removed from the dry box. The reactor was charged with hydrogen to 1900 psi and heated to 65° C. After stirring for 48 hours the mixture was opened to air and concentrated. The residue was diluted with diethyl ether (20 mL) and extracted with 1N HCl (3×10 mL). The combined aqueous layers were basified with NaOH until strongly basic to pH paper and extracted with diethyl ether (4×25 mL). The organic layers were combined, dried over sodium sulfate and concentrated to produce 82-89% yield of N-benzyl-1-phenylethylamine. The enantiomeric excess (ee), as determined by HPLC analysis of the free amine using a Chiralcel OD column, was 89-92% in favor of the (R)enantiomer. In a dry Schlenk tube under argon was placed the mixture was stirred for another 10 minutes the reaction vessel was sealed moved to a dry box was sealed removed from the dry box The reactor was charged with hydrogen to 1900 psi After stirring for 48 hours the mixture concentrated The residue was diluted with diethyl ether (20 mL) extracted with 1N HCl (3×10 mL) extracted with diethyl ether (4×25 mL) dried over sodium sulfate concentrated

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The process is carried out as in Example 8 but the reaction conditions are modified as follows: 0.636 g (4.8 mmol) of N-benzyl-N-(1-phenylethylidene)amine, 3.2 mg (0.0048 mmol) of [Ir(1,5-cyclooctadiene)Cl]2, 4.5 mg (0.01 mmol) of 1,4-bis(diphenylphosphino)butane (ligand) and 30 mg (0.08 mmol) of tetrabutylammonium iodide, 2 ml of acetic acid, 5 ml of toluene, 40 bar of hydrogen, reaction temperature: 25° C. The reaction time is 2 hours, the conversion is complete. the reaction conditions 25° C

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The process is carried out as in Example 6, but the reaction conditions are modified as follows: 0.636 g (3 mmol) of N-benzyl-N-(1-phenylethylidene)amine, 10.2 mg (0.0152 mmol) of [Ir(1,5-cyclooctadiene)Cl]2, 21.4 mg (0.0333 mmol) of {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethylphenyl)phosphine (ligand) and 15 mg (0.04 mmol) of tetrabutylammonium iodide, 2 ml of acetic acid, 15 ml of toluene, 30 bar of hydrogen, reaction temperature: 25° C. The reaction time is 20 minutes. The conversion is complete, the ee 31%. the reaction conditions 25° C

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: N-Benzyl-1-phenylethanimine (0.11 g, 0.5 mmol) and each metal complex (0.005 mmol) were weighed in a Pyrex (registered trade name) test tube for autoclaving, the tube was set in a 50-mL autoclave together with a stirrer in the tube, and the atmosphere in the autoclave was substituted with nitrogen. The mixture was added with 2 mL of methanol and EtsN (14 μL, 0.1 mmol), the atmosphere in the autoclave was sufficiently substituted with hydrogen, and then pressurized with 5.0 MPa of hydrogen, and the reaction was allowed at 40° C. for 24 hours. After the reaction, the reaction mixture was added with 0.02 g of activated carbon and stirred for 30 minutes, and after the activated carbon was removed, the reaction mixture was concentrated in an evaporator to quantitatively obtain optically active N-benzyl-1-phenylethylamine. the tube was set in a 50-mL autoclave together with a stirrer in the tube After the reaction the reaction mixture was added with 0.02 g of activated carbon after the activated carbon was removed the reaction mixture was concentrated in an evaporator

反应条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 500 ml pressure reactor, N-benzyl-(1-phenylethylidene)-amine 68 mg (0.32 mmol), tristriphenylphosphine rhodium (I) chloride 6 mg (0.0065 mmol), 3,3-dimethyl-1-butene 27 mg (0.32 mmol) were placed and dissolved in toluene 100 mg. While the reactor was stopped with a stopper, the reactants were heated at 150° C. for 2 hours with stirring. After completion of the reaction, the reactant mixture was dissolved in THF 3 ml and then combined with 1 N HCl soln. 10 ml, followed by hydrolysis with stirring for 12 hours at room temperature. After the mixture was three times extracted with Et2O and CH2Cl2, the organic layer was dried over MgSO4 and then filtered and the solvent was evaporated under reduced pressure. The reactant mixture of the organic layer was purified by column chromatography on silica gel (5:2 hexane:ethyl acetate) to obtain 2-(3,3-dimethylbutyl)phenyl-1-ethanone 64 mg (0.31 mmol). Yield: 97%. Under the same conditions, a variety of olefins were employed, and the results are given in Table 1, below. After completion of the reaction 10 ml, followed by hydrolysis with stirring for 12 hours at room temperature extracted with Et2O and CH2Cl2 the organic layer was dried over MgSO4 filtered the solvent was evaporated under reduced pressure The reactant mixture of the organic layer was purified by column chromatography on silica gel (5:2 hexane:ethyl acetate)