Desulfurative Chlorination of Alkyl Phenyl Sulfides

Abstract

The chlorination of readily available secondary and tertiary alkyl phenyl sulfides using (dichloroiodo)­benzene (PhICl₂) is reported. This mild and rapid nucleophilic chlorination is extended to sulfa-Michael derived sulfides, affording elimination-sensitive β-chloro carbonyl and nitro compounds in good yields. The chlorination of enantioenriched benzylic sulfides to the corresponding inverted chlorides proceeds with high stereospecificity, thus providing a formal entry into enantioenriched chloro-Michael adducts. A mechanism implying the formation of a dichloro-λ⁴-sulfurane intermediate is proposed