The chlorination of readily available secondary and tertiary alkyl phenyl sulfides using (dichloroiodo)benzene (PhICl) 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-λ-sulfurane intermediate is proposed.

Molecular bromine is shown to stereoselectively brominate readily available alkyl phenyl sulphides under exceptionally mild reaction conditions.

The aim of this opinion article is to highlight the trends in the development of efficient catalyst-free synthesis of the Hantzsch polysubstituted 1,3-thiazoles. They are heterocycles of particular importance in the pharmaceutical industry, and the strategy involves the cyclization reaction of acyclic precursors with minimum auxiliary substances, toxic reagents, organic solvents, and disposal problems.