Synthesis of benzylic thioether containing α-substituted thio compounds via carbene insertion into an S-H bond: expeditious access to a new C-S bond.

Considering the importance of thioethers in biological systems, we developed a strategy to achieve these target molecules. In this regard, an efficient copper(ii)-catalyzed synthesis of highly biologically relevant thioethers is realized, employing readily available and inexpensive starting precursors under ambient conditions. The developed new methodology is very useful to selectively synthesize a C-S bond via carbene insertion into an S-H bond. Our strategy also paved the way to produce a wide range of α-thio substituted benzylic esters in a single-pot method in very good yields under short reaction times. All the synthesized compounds have been fully characterized using spectroscopic and analytical techniques. The best features of the developed strategy are S-H insertion, mild reaction conditions, wide substrate scope, and excellent functional group tolerance.