Abstract
Crystallization-Induced Diastereomer Transformation (CIDT) of α-bromo-α′-(R)-sulfinylketones is reported. This process provides not readily accessible enantiopure stereolabile αbromoketones, which after diastereoselective carbonyl group reduction lead to the corresponding highly value-added anti and syn-bromohydrins with excellent diastereoselectivities. As an application, a diastereodivergent synthesis of enantiopure hemlock alkaloid (+)-α-conhydrine and its diastereomer (-)-β-conhydrine is also described.