Halogen Cation Induced Stereoselective Semipinacol-type Rearrangement of Allylic Alcohols: A Highly Efficient Approach to α-Quaternary β-Haloketo Compounds

Abstract Allylic alcohols were found to undergo a semipinacol-type rearrangement induced by halogen cation generated from the chloramine-T/ZnX 2 combination, which provided a highly efficient and stereoselective method for the preparation of α-quaternary β-haloketo compounds. This reaction is valuable and versatile since a quaternary carbon could be constructed effectively and three kinds of β-haloketo compounds (X = Cl, Br, I) could be achieved readily.