1-phenyl-N-trimethylsilylmethanamine

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

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

Conditions: temp:26.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (8.45 g, 0.132 mol) in hexane was added to a solution of tetramethylethylenediamine (15.3 g, 0.132 mol) in 60 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-trimethylsilylbenzylamine (10.8 g, 0.06 mol) in 30 ml. of anhydrous cyclohexane was added to the reaction mixture to produce a suspension containing a dilithio compound. This suspension was stirred for 16 hours at 26° C. and then was dropwise added to a solution of phenylphosphonic dichloride (12.5 g, 0.064 mol) in 120 ml. of anhydrous cyclohexane over a period of 1 hour at 26° C. After stirring for 2 hours, the reaction mixture was partitioned in methylene chloride and water. The layers were separated and the methylene chloride layer was washed with water, dried over sodium sulfate and then concentrated in vacuo to yield an oil. The oil was chromatographically separated on a silica gel column using ethyl acetate as the eluant. Fractions containing the benzazaphosphole were combined and concentrated in vacuo to produce a crude product. The crude product was crystallized from petroleum ether to yield 1-phenyl-2-(trimethylsilyl)-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide as a crystalline solid. A second crop was obtained to give a total yield of 2.45 g, 14% yield to yield 1-phenyl-2-(trimethylsilyl)-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide having a melting point of 90°-94° C. and the following analysis: While maintaining the temperature of the reaction at 0° C. to produce a suspension After stirring for 2 hours the reaction mixture was partitioned in methylene chloride The layers were separated the methylene chloride layer was washed with water dried over sodium sulfate concentrated in vacuo to yield an oil The oil was chromatographically separated on a silica gel column Fractions containing the benzazaphosphole concentrated in vacuo to produce a crude product The crude product was crystallized from petroleum ether

Conditions: temp:26.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (8 g, 0.125 mol) in hexane was added to a solution of tetramethylethylenediamine (14.3 g, 0.123 mol) in 60 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-trimethylsilylbenzylamine (10.75 g, 0.06 mol) in 60 ml. of anhydrous cyclohexane was added to the reaction mixture to produce a suspension containing a dilithio compound. This suspension was stirred for 16.5 hours at 26° C. and then cooled to -72° C. using a solid carbon dioxide-acetone bath. A solution of isopropylphosphonic dichloride (10.3 g, 0.064 mol) in 60 ml. of anhydrous cyclohexane was rapidly added to the suspension causing the temperature of the reaction to increase to -10° C. The reaction mixture was allowed to cool to -72° C., after which time the solid carbon dioxide-acetone bath was removed and the reaction mixture was stirred for 1.5 hours at 26° C. The reaction mixture was cooled to 0° C. and then quenched with the rapid addition of 12 ml. of acetic acid. The reaction mixture was concentrated under vacuum and the resulting residue was partitioned between methylene chloride and water. The layers were separated and the methylene chloride layer was dried over magnesium sulfate and concentrated in vacuo to yield a red oil. The red oil was distilled at 180° C. and 0.2 mm to yield 1-isopropyl-2-trimethylsilyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide. While maintaining the temperature of the reaction at 0° C. to produce a suspension cooled to -72° C. the temperature of the reaction to increase to -10° C to cool to -72° C. after which time the solid carbon dioxide-acetone bath was removed the reaction mixture was stirred for 1.5 hours at 26° C The reaction mixture was cooled to 0° C. quenched with the rapid addition of 12 ml The reaction mixture was concentrated under vacuum the resulting residue was partitioned between methylene chloride and water The layers were separated the methylene chloride layer was dried over magnesium sulfate concentrated in vacuo to yield a red oil The red oil was distilled at 180° C.

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

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

Conditions: temp:26.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (16 g, 0.25 mol) in hexane was added to a solution of tetramethylethylenediamine (28.6 g, 0.246 mol) in 120 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-trimethylsilylbenzylamine (21.6 g, 0.12 mol) in 60 ml. of anhydrous cyclohexane was added to the reaction mixture to produce a suspension containing a dilithio compound. This suspension was stirred for 16 hours at 26° C. and then cooled to -76° C. using a solid carbon dioxide-acetone bath. A solution of phenylphosphonic dichloride (25 g, 0.128 mol) in 120 ml. of anhydrous cyclohexane was rapidly added to the suspension causing the temperature of the reaction to increase to -15° C. The reaction mixture was allowed to cool to -76° C., after which time the solid carbon dioxide-acetone bath was removed and the reaction mixture was stirred for 3 hours. The reaction mixture was cooled to 0° C., then quenched with the rapid addition of 24 ml. of acetic acid. After stirring the reaction mixture for 5 minutes, the cyclohexane was removed on a rotary evaporator, and the resulting residue was partitioned between methylene chloride and water. The layers were separated and the methylene chloride layer was dried over magnesium sulfate and concentrated in vacuo to yield an oil. Distillation of this oil at 180° C. and 0.3 mm yielded 1-phenyl-2-trimethylsilyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide. While maintaining the temperature of the reaction at 0° C. to produce a suspension cooled to -76° C. the temperature of the reaction to increase to -15° C to cool to -76° C. after which time the solid carbon dioxide-acetone bath was removed the reaction mixture was stirred for 3 hours The reaction mixture was cooled to 0° C. quenched with the rapid addition of 24 ml After stirring the reaction mixture for 5 minutes the cyclohexane was removed on a rotary evaporator the resulting residue was partitioned between methylene chloride and water The layers were separated the methylene chloride layer was dried over magnesium sulfate concentrated in vacuo to yield an oil Distillation of this oil at 180° C.

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

Procedure: To a solution of 4.53 mmol of LDA at -78° (generated by adding a 3 ml of 1.55M n-butyllithium in n-hexane to 0.33 g of diethylamine in 5 ml of THF) was added 1.0 g (4.52 mmol) of N,N-diethyl-3-methoxy-2-methylbenzamide in 10 ml THF. Then a solution of 4.53 mmol of trimethylsilyl benzylamine [generated from 0.81 (4.53 mmol) of hexamethyldisilazane in 2 ml of n-hexane added to 3 ml of 1.55N n-butyllithium followed by the addition of 0.48 g (4.53 mmol) of benzaldehyde in 2 ml of n-hexane] was added and stirring continued at -78° for two hours and then at room temperature for one hour. The reaction was cooled to 0° and 50 ml of 1N HCl was added. The red-purple solution became yellow. The mixture was extracted with ether, the ether extracts were washed with 1N HCl, dried (MgSO4), and concentrated. The residue was triturated with ethanol to give 0.17 g (15%) of product; mp 227°-231°. at -78° was added at room temperature for one hour The reaction was cooled to 0° The mixture was extracted with ether the ether extracts were washed with 1N HCl dried (MgSO4) concentrated The residue was triturated with ethanol

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

Procedure: Under an argon atmosphere, n-butyllithium (0.9 mL, 1.6 M in hexane solution, 1.5 mmol) was added to a solution of N-benzyltrimethylsilylamine (0.3 mL, 1.5 mmol) in toluene (4 mL) at −78° C. over 5 min. After stirring for 0.5 hr, a solution of (1R,2R)-1,2-dimethoxy-1,2-diphenylethane (436 mg, 1.8 mmol) in toluene (2 mL) was added, and the mixture was stirred at −78° C. for 0.5 hr. Thereto was added a solution of tert-butyl cinnamate (204 mg, 1.0 mmol) and chlorotrimethylsilane (0.63 mL, 5.0 mmol) in toluene (2 mL) over 5 min. The mixture was stirred at −78° C. for 5 hr, and quenched with saturated aqueous ammonium chloride solution (1.5 mL). After adding a saturated aqueous sodium hydrogen carbonate solution (20 mL), the mixture was extracted with ethyl acetate. The organic layer was washed with brine and dried over sodium sulfate, after which it was concentrated and subjected to silica gel column chromatography (ethyl acetate/hexane=1/25) to give the title compound (302 mg, yield 97%) as a colorless oil of [α]25D+32.5 (c 1.35, CHCl3). the mixture was stirred at −78° C. for 0.5 hr The mixture was stirred at −78° C. for 5 hr quenched with saturated aqueous ammonium chloride solution (1.5 mL) After adding a saturated aqueous sodium hydrogen carbonate solution (20 mL) the mixture was extracted with ethyl acetate The organic layer was washed with brine dried over sodium sulfate after which it was concentrated