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A silver‐catalyzed biomimetic transfer hydrogenation of N‐heteroaromatics with Hantzsch esters as NADH analogues has been developed. The reaction proceeded smoothly under mild conditions to give the corresponding reductive products in up to 99% yield. The asymmetric version of this reaction was also conducted preliminarily with up to 66% ee.

An exclusive asymmetric reduction of C=O of 2-arylidene four-, five-, six-, and seven-membered cycloalkanones has been studied systematically. The asymmetric transfer hydrogenation was performed using robust and commercially available chiral...