Reactivity of α‐Bromosulfones Obtained from gem‐Dibromides

Abstract

α‐Bromosulfones have been synthesized diastereoselectively by reaction of β‐hydroxy gem‐dibromides with aromatic sulfinates. More steric demanding groups in the β‐position led to increased stereoselectivity in these SN2 reactions. Lithiated α‐bromosulfones react diastereoselectively with alkylating agents, aldehydes, and ketones. No configurational stability of the lithiated α‐bromosulfones was observed except fast equilibration towards a chelate‐stabilized intermediate. Treatment of the α‐bromosulfone with methylcuprate resulted in substitution of the bromine by a methyl group.