Methyl acetoacetate → methyl (3R)-3-aminobutanoate acetate

Participants

Reaction Conditions

Reaction Steps

Ru(OCOCH3)2((R)-dm-binap) (164.3 mg, 0.1722 mmol), methyl acetoacetate (10.00 g, 86.12 mmol), ammonium acetate (6.64 g, 86.12 mmol) and methanol (50 mL) were placed in a stainless steel autoclave under nitrogen atmosphere, and the mixture was stirred at 80° C. under a hydrogen pressure of 3 MPa for 15 hours. After completion of the reaction, the solvent was removed by evaporation to give methyl (3R)-3-aminobutanoate acetate as a crude material (16.29 g). The crude product was treated with 7N ammonia/methanol and analyzed by GLC analysis using a capillary column TC-5HT (available from GL SCIENCES CO.), indicating that the yield of methyl 3-aminobutanoate was 86.4%, that of the by-produced methyl 3-hydroxybutanoate was 0.7%, that of the by-produced methyl 3-aminocrotonate was 1.4% and that of the by-produced methyl 3-(2-methoxycarbonyl-1-methyl-ethylamino)-2-butenoate was 6.2%. The enantiomeric excess of methyl (3R)-3-aminobutanoate in the crude product was found to be 81.9% ee by HPLC analysis using a CHIRALCEL OD-H column after conversion into methyl (3R)-3-(4-nitrobenzoylamino)butanoate.

Provenance & Evidence