Palladium-Catalyzed Insertion of Isocyanides into the C-S Bonds of Heteroaryl Sulfides.

Insertion of tert-butyl isocyanide into the C(sp2 )-S bonds of heteroaryl sulfides is catalyzed by a palladium diphosphine complex. Thioimidates generated through this reaction could be readily hydrolyzed under acidic conditions to yield the corresponding thioesters, which are of synthetic use. This insertion is useful because starting heteroaryl sulfides were readily prepared by either conventional ways or through sulfur-specific extended Pummerer reactions.