The development of biomimetic chemistry based on the NAD(P)H with hydrogen gas as terminal reductant is a long-standing challenge. Through rational design of the chiral and regenerable NAD(P)H analogues based on planarchiral ferrocene,abiomimetic asymmetric reduction has been realized using bench-stable Lewis acids as transfer catalysts. A broad set of alkenes and imines could be reduced with up to 98% yield and 98% ee, likely enabled by enzyme-like cooperative bifunctional activation. This reaction represents the first general biomimetic asymmetric reduction (BMAR) process enabled by chiral and regenerable NAD(P)H analogues. This concept demonstrates catalytic utility of a chiral coenzyme NAD(P)H in asymmetric catalysis.
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