Recent advances in thiolation via sulfur electrophiles

Umpolung of thiols has become a common strategy for the synthesis of various S-containing compounds and thus a series of sulfur electrophiles have been designed and applied for diverse thiolations. To meet different demands for the incorporation of thio groups with regio- and stereoselectivity, new catalyst systems and methodologies based on the utility of sulfur electrophiles have been well developed. In this review, achievements on various thiolation methodologies with sulfur electrophiles have been summarized, mainly including thiofunctionalization of alkenes or alkynes, insertion of carbene precursors, C-S cross coupling and electrophilic substitution, aiming to give a comprehensive insight into the application of electrophilic sulfur reagents.