Asymmetric Synthesis of Tertiary Thiols

Significance

A base-promoted rearrangement of substituted thiocarbamates is disclosed. Following up on their earlier work with N-aryl carbamates (J. Am. Chem. Soc. 2009, 131, 3410), the authors use this strategy to synthesize the much less accessible tertiary thiols. By utilizing chiral thiocarbamate substrates, the rearrangement occurs with retention of stereochemistry, yielding enantiomerically enriched tertiary thiols.