Preparation of chiral primary amine through asymmetric reductive amination of simple ketone under catalytic action of ruthenium-diphosphine catalyst
A technology for catalysts and primary amines, applied in the field of preparation of chiral primary amines
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Embodiment 1
[0061] In argon atmosphere, acetophenone (1mmol, 120mg), RuX 2 L, NH 4 X (2mmol) was added to a 5mL ampoule, and the corresponding solvent (2mL) was added, the reaction bottle was placed in an autoclave, and the hydrogen gas was flushed three times, each time filled with 10atm hydrogen gas, and the required hydrogen gas was flushed in the last time pressure, put the autoclave in an oil bath preheated to the corresponding temperature in advance, heat and stir for 24 hours, cool to room temperature, slowly release hydrogen, take out the reaction bottle, add 3mL of 6M hydrogen chloride solution, and heat at 80°C for 6 hours , cooled, washed twice with ether, neutralized to pH 10 with 4M sodium hydroxide solution, extracted three times with ether, combined organic phases, dried over anhydrous sodium sulfate, and dried in vacuo to obtain pure 1-phenylethylamine, the product The determination of enantioselectivity needs to acetylate the product first, and the corresponding yield an...
Embodiment 2
[0065] Compared with Entry 18 in Example 1, the post-treatment did not add 6M hydrochloric acid solution for heat treatment.
[0066]
[0067] In argon atmosphere, acetophenone (1mmol, 120mg), Ru(OAc) 2 L 1 (0.1mol%), NH 4 OAc (2mmol, 154mg) and trifluoroethanol (2mL) were added in a 5mL ampoule, the reaction bottle was placed in an autoclave, and the hydrogen gas was flushed three times, each filling 10atm of hydrogen, and the last time was flushed into 50atm. The autoclave is placed in an oil bath preheated to the corresponding temperature in advance, heated to 120°C and stirred for 24 hours, cooled to room temperature, slowly releasing hydrogen, taking out the reaction bottle, cooled, washed twice with diethyl ether, and oxidized with 4M hydroxide The sodium solution was neutralized to pH 10, extracted three times with ether, the organic phases were combined, dried over anhydrous sodium sulfate, and vacuum-dried to obtain pure (R)-1-phenylethan-1-amine, 97mg, 81% yield...
Embodiment 3
[0069]
[0070] In an argon atmosphere, 4-methylacetophenone (1mmol, 134mg), Ru(OAc) 2 L 5 (0.5mol%), NH 4 OAc (2mmol, 154mg) and trifluoroethanol (2mL) were added in a 5mL ampoule, the reaction bottle was placed in an autoclave, and the hydrogen gas was flushed three times, each filling 10atm of hydrogen, and the last time was flushed into 50atm. The autoclave was placed in an oil bath preheated to the corresponding temperature in advance, heated for 20 hours with stirring, cooled to room temperature, and slowly released hydrogen gas, took out the reaction bottle, added 3 mL of 6M hydrogen chloride solution, heated at 80°C for 6 hours, cooled, Wash twice with ether, neutralize to pH 10 with 4M sodium hydroxide solution, extract three times with ether, combine organic phases, dry over anhydrous sodium sulfate, and dry in vacuo to obtain pure (R)-1-(p-tolyl ) ethan-1-amine, 117 mg, 87% yield, 96% ee.
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