Science of Synthesis

Geertsema, E. M.; Poelarends, G. J., Science of Synthesis: Biocatalysis in Organic Synthesis, (2015) 2, 323.

Besides the Michael addition of α-nitro carbonyl donors to an α,β-unsaturated carbonyl acceptor (see Section ‌2.3.4.1.4‌) and the Michael-type addition of 1,3-dicarbonyl donors to (E)-(2-nitrovinyl)benzene (see Section ‌2.3.4.2.1‌), immobilized C. antarctica lipase A (CALA) has also been reported to catalyze the addition of α-nitro carbonyl donors ‌16‌ to (E)-(2-nitrovinyl)benzene (‌Scheme 6‌).[‌54‌] CALA-catalyzed conversions of (E)-(2-nitrovinyl)benzene of 67 and 34% are observed in the presence of donors methyl 2-nitroacetate (‌16‌, R1 = H) and methyl 2-nitropropanoate (‌16‌, R1 = Me), respectively. The addition of methyl 2-nitroacetate (‌16‌, R1 = H) to (E)-(2-nitrovinyl)benzene is also catalyzed by immobilized C. antarctica lipase B (CALB; 2.5 and 1.6% w/w) and lipase from M. miehei (MML; 1.6% w/w). Conversions of (E)-(2-nitrovinyl)benzene of 91 (2.5% w/w CALB), 40 (1.6% w/w CALB), and 89% (1.6% w/w MML) have been established, respectively. These three enzyme systems do not show any significant activity for the addition of methyl 2-nitropropanoate (‌16‌, R1 = Me) to (E)-(2-nitrovinyl)benzene. In the reactions catalyzed by CALA and CALB, low diastereoselectivity (up to 9% de) and no enantioselectivity (0% ee) are reported for products ‌17‌.

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