Asymmetric hydroazidation of α-substituted vinyl ketones catalyzed by chiral primary amine

We report herein the first example of asymmetric hydroazidation of a-substituted vinyl ketones by using chiral primary amines as the catalysts. A simple chiral primary-tertiary diamine catalyst derived from phenylalanine was found to readily promote this aza-Michael addition reaction with enamine protonation as the key stereogenic step, thus enabling the effective synthesis of a-chiral beta-azido ketones with good yields and moderate enantioselectivities. (C) 2017 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.