N-(1-phenylethyl)aniline

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: According to the general procedure, a solution of N-(1-phenylethylidene)aniline (50 mg, 0.26 mmol) and rac-32 (7.8 mg, 0.0050 mmol, 1.9 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 42 as a clear oil (41 mg, 81%). 1H NMR28 (300 MHz, CDCl3): δ 7.50-7.35 (m, 4H), 7.30-7.25 (m, 1H), 7.15 (t, 2H, J=7.5 Hz), 6.70 (t, 1H, J=7.5 Hz), 6.59 (d, 2H, J=7.5 Hz), 4.56 (quin, 1H, J=6.6 Hz), 4.08 (bs, 1H), 1.56 (d, 3H, J=6.6 Hz); 13C NMR (75.5 MHz, CDCl3): δ 147.4, 145.4, 129.3, 128.8, 127.0, 126.0, 117.4, 113.4, 53.6, 25.2. Filtration of the reaction mixture and evaporation of the solvent

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

Procedure: The general procedure under argon was followed using copper(I) iodide (10 mg, 0.05 mmol), K3PO4 (425 mg, 2.00 mmol), α-methylbenzylamine (155 μL, 1.20 mmol), iodobenzene (112 μL, 1.00 mmol), ethylene glycol (111 μL, 2.00 mmol) and 2-propanol (1.0 mL). Column chromatography using a solvent mixture (hexane/ethyl acetate=20/1, Rf=0.5) afforded N-(phenyl)-α-methylbenzylamine (144 mg, 73% isolated yield) as colorless liquid. HPLC conditions: (column: Daicel OD-H; solvent: 10% iPrOH in hexane; flow rate: 0.7 mL/min; UV lamp: 254 nm; retention time: 6.01, 6.78 min). The spectral data (1H NMR) matched with the literature references and GC analysis indicated >95% purity. See Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A. J. Am. Chem. Soc. 1999, 121, 6421-6429.

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

Procedure: The general procedure under argon was followed using copper(I) iodide (10 mg, 0.05 mmol), K3PO4 (425 mg, 2.00 mmol), α-methylbenzylamine (155 μL, 1.20 mmol), iodobenzene (112 μL, 1.00 mmol), ethylene glycol (111 μL, 2.00 mmol) and 2-propanol (1.0 mL). Column chromatography using a solvent mixture (hexane/ethyl acetate=20/1, Rf=0.5) afforded N-(phenyl)-α-methylbenzylamine (144 mg, 73% isolated yield) as colorless liquid. HPLC conditions: (column: Daicel OD-H; solvent: 10% iPrOH in hexane; flow rate: 0.7 mL/min; UV lamp: 254 nm; retention time: 6.01, 6.78 min). The spectral data (1H NMR) matched with the literature references and GC analysis indicated >95% purity. See Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A. J. Am. Chem. Soc. 1999, 121, 6421-6429.

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The reaction was carried out in a multiwell hydrogenation vessel. Dichloro-{1,2-Bis[(2R,5R)-2,5-diphenylphospholano]methane}[(1S,2S)-1,2-diphenylethylenediamine)] ruthenium (II) (2.2 mg, 0.0025 mmol) was suspended in degassed isopropanol (2 ml) in a Schlenk flask under nitrogen. Added potassium tert-butoxide (1M in tert-butanol, 0.025 ml) and heated until a yellow solution was obtained. The glass liner was charged with N-(1-phenylethylidene)aniline (98 mg, 0.50 mmol). Charged to 10 bar nitrogen and vented (×5). Added the precatalyst solution and charged to 10 bar nitrogen and vented (×2). Commenced stirring at 1000 rpm and heated to 60° C. Charged to 10 bar H2 and stirred for 18 h. Cooled to room temperature, vented and evaporated to give phenyl-(1-phenylethyl)amine, conversion>99%, ee 71% (GC, sample derivatised by treatment with acetic anhydride pyridine, Chirasil DEX CB, 25 m×0.25 mm, injector/detector 200° C., helium 20 psi, 140° C. for 20 minutes then ramp at 5° C./min to 200° C., hold for 5 minutes, retention times 23.21 minutes and 23.45 minutes). The reaction was carried out in a multiwell hydrogenation vessel was obtained Charged to 10 bar nitrogen Added the precatalyst solution charged to 10 bar nitrogen Charged to 10 bar H2 stirred for 18 h Cooled to room temperature evaporated

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The reaction was carried out in a multiwell hydrogenation vessel. Dichloro-{1,2-Bis[(2R,5R)-2,5-diphenylphospholano]methane}[(1S,2S)-1,2-diphenylethylenediamine)] ruthenium (II) (2.2 mg, 0.0025 mmol) was suspended in degassed isopropanol (2 ml) in a Schlenk flask under nitrogen. Added potassium tert-butoxide (1M in tert-butanol, 0.025 ml) and heated until a yellow solution was obtained. The glass liner was charged with N-(1-phenylethylidene)aniline (98 mg, 0.50 mmol). Charged to 10 bar nitrogen and vented (×5). Added the precatalyst solution and charged to 10 bar nitrogen and vented (×2). Commenced stirring at 1000 rpm and heated to 60° C. Charged to 10 bar H2 and stirred for 18 h. Cooled to room temperature, vented and evaporated to give phenyl-(1-phenylethyl)amine, conversion>99%, ee 71% (GC, sample derivatised by treatment with acetic anhydride pyridine, Chirasil DEX CB, 25 m×0.25 mm, injector/detector 200° C., helium 20 psi, 140° C. for 20 minutes then ramp at 5° C./min to 200° C., hold for 5 minutes, retention times 23.21 minutes and 23.45 minutes). The reaction was carried out in a multiwell hydrogenation vessel was obtained Charged to 10 bar nitrogen Added the precatalyst solution charged to 10 bar nitrogen Charged to 10 bar H2 stirred for 18 h Cooled to room temperature evaporated

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

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

Procedure: The general procedure under argon was followed using copper(I) iodide (10 mg, 0.05 mmol), K3PO4 (425 mg, 2.00 mmol), α-methylbenzylamine (155 μL, 1.20 mmol), iodobenzene (112 μL, 1.00 mmol), ethylene glycol (111 μL, 2.00 mmol) and 2-propanol (1.0 mL). Column chromatography using a solvent mixture (hexane/ethyl acetate=20/1, Rf=0.5) afforded N-(phenyl)-α-methylbenzylamine (144 mg, 73% isolated yield) as colorless liquid. HPLC conditions: (column: Daicel OD-H; solvent: 10% iPrOH in hexane; flow rate: 0.7 mL/min; UV lamp: 254 nm; retention time: 6.01, 6.78 min). The spectral data (1H NMR) matched with the literature references and GC analysis indicated >95% purity. See Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A. J. Am. Chem. Soc. 1999, 121, 6421-6429.

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

Procedure: The general procedure under argon was followed using copper(I) iodide (10 mg, 0.05 mmol), K3PO4 (425 mg, 2.00 mmol), (α-methylbenzylamine (155 μL, 1.20 mmol), iodobenzene (112 μL, 1.00 mmol), ethylene glycol (111 μL, 2.00 mmol) and 2-propanol (1.0 mL). Column chromatography using a solvent mixture (hexane/ethyl acetate=20/1, Rƒ=0.5) afforded N-(phenyl)-α-methylbenzylamine (144 mg, 73% isolated yield) as colorless liquid. HPLC conditions: (column: Daicel OD-H; solvent: 10% PrOH in hexane; flow rate: 0.7 mL/min; UV lamp: 254 nm; retention time: 6.01, 6.78 min). The spectral data (1H NMR) matched with the literature references and GC analysis indicated >95% purity. See Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A. J. Am. Chem. Soc. 1999, 121, 6421-6429.

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

Procedure: The general procedure under argon was followed using copper(I) iodide (10 mg, 0.05 mmol), K3PO4 (425 mg, 2.00 mmol), α-methylbenzylamine (155 μL, 1.20 mmol), iodobenzene (112 μL, 1.00 mmol), ethylene glycol (111 μL, 2.00 mmol) and 2-propanol (1.0 mL). Column chromatography using a solvent mixture (hexane/ethyl acetate=20/1, Rf=0.5) afforded N-(phenyl)-α-methylbenzylamine (144 mg, 73% isolated yield) as colorless liquid. HPLC conditions: (column: Daicel OD-H; solvent: 10% iPrOH in hexane; flow rate: 0.7 mL/min; UV lamp: 254 nm; retention time: 6.01, 6.78 min). The spectral data (1H NMR) matched with the literature references and GC analysis indicated >95% purity. See Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A. J. Am. Chem. Soc. 1999, 121, 6421–6429.

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

Procedure: According to the general procedure, a solution of N-(1-phenylethylidene)aniline (50 mg, 0.26 mmol) and rac-32 (7.8 mg, 0.0050 mmol, 1.9 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 42 as a clear oil (41 mg, 81%). 1H NMR28 (300 MHz, CDCl3): δ 7.50-7.35 (m, 4H), 7.30-7.25 (m, 1H), 7.15 (t, 2H, J=7.5 Hz), 6.70 (t, 1H, J=7.5 Hz), 6.59 (d, 2H, J=7.5 Hz), 4.56 (quin, 1H, J=6.6 Hz), 4.08 (bs, 1H), 1.56 (d, 3H, J=6.6 Hz); 13C NMR (75.5 MHz, CDCl3): δ 147.4, 145.4, 129.3, 128.8, 127.0, 126.0, 117.4, 113.4, 53.6, 25.2. Filtration of the reaction mixture and evaporation of the solvent