Catalytic Stereospecific Substitution of Enantioenriched Allylic Alcohols with Sodium Sulfinates

An unprecedented stereospecific substitution reaction of enantioenriched allylic alcohols with sodium sulfinates has been developed for the asymmetric synthesis of allylic sulfones with excellent ee. A range of highly enantioenriched allylic alcohols smoothly underwent palladium diacetate/racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthylcatalyzed substitution with sodium sulfinates to give structurally diverse a-chiral allylic sulfones in moderate to excellent yields with complete retention of configuration. This study paves the way for the direct stereospecific substitution of enantioenriched allylic alcohols with sulfur nucleophiles.