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Preparation of Optically Active Biphenyl Compounds via an Albumin- Mediated Asymmetric Nitroaldol Reaction

Author(s):

Kazutsugu Matsumoto*, Ryota Kitabayashi, Naoki Fukuchi and Noriyuki Suka   Pages 1 - 8 ( 8 )

Abstract:


Human serum albumin (HSA) was found to catalyze the asymmetric nitroaldol reaction of biphenyl aldehydes with nitromethane to afford the corresponding optically active 2-nitro alcohols. Careful optimization of the conditions for the reaction of 4-phenylbenzaldehyde with nitromethane in water at a neutral pH improved both the reactivity and the enantioselectivity. Finally, the reaction of 4-phenylbenzaldehyde (56 mg, 0.30 mmol) in nitromethane (2.8 mL) and water (1.1 mL) using HSA (68 mg) at 5 °C for 240 h gave (R)-1-([1,1'-biphenyl]-4-yl)-2-nitroethanol in 71% yield (52 mg), with an ee up to 85% ee. Subsequent recrystallization improved the ee up to 95%. The reaction was useful in a preparative-scale operation, and the biocatalyst could be reused several times. The procedure was also applicable to other substrates with different substitution patterns. Although the nitroaldol reaction of 2-phenylbenzaldehyde with nitromethane proceeded with low enantioselectivity to afford the corresponding (R)-2-nitroalcohols (35% ee), the reactions of the substrates bearing Br, Me, OMe, or CN group at the 4'-position of the benzene ring gave the corresponding optically active compounds with high enantioselectivities (80-88% ee).

Keywords:

Asymmetric nitroaldol reaction, biocatalysis, human serum albumin, 2-nitro alcohols, optically active biaryl compounds, reaction in water.

Affiliation:

Department of Chemistry and Life Science, Meisei University, 2-1-1 Hodokubo, Hino, Tokyo 191-8506, Department of Chemistry and Life Science, Meisei University, 2-1-1 Hodokubo, Hino, Tokyo 191-8506, Department of Chemistry and Life Science, Meisei University, 2-1-1 Hodokubo, Hino, Tokyo 191-8506, Department of Chemistry and Life Science, Meisei University, 2-1-1 Hodokubo, Hino, Tokyo 191-8506



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