Abstract
Crystallization‐Induced Diastereomer Transformation (CIDT) of α ‐bromo‐ α ’‐( R )‐sulfinylketones is reported. The utility of these 1,2‐difunctionalized synthons is convincingly demonstrated by their facile conversion into cyanohydrins and bromohydrins. Furthermore, bromohydrins can be converted into complex arrangements of functionality and stereochemistry through S N 2‐like inter and intramolecular transformations.