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

We report herein the first example of asymmetric hydroazidation of α-substituted vinyl ketones by using chiral primary amines as the catalysts. A simple chiral primary-tertiary diamine catalyst derived from l-phenylalanine was found to promote this aza-Michael addition reaction with enamine protonation as the key stereogenic step, thus enabling the effective synthesis of α-chiral β-azido ketones with good yields and moderate enantioselectivities.