Enantioselective synthesis of tertiary thiols by intramolecular arylation of lithiated thiocarbamates

Lithiation of N-aryl S-alpha-alkylbenzyl thiocarbamates leads to rearrangement with migration of the N-aryl ring to the anionic centre a to S, a process which generally proceeds with ca. 98% retention of stereochemistry and returns chiral benzylic tertiary thiols in high enantiomeric ratios.