Stereoselective Synthesis ofZ-Styryl Sulfides from Nucleophilic Addition of Arylacetylenes and Benzyl Thiols

The stereoselective synthesis of Z-anti-Markovnikov styryl sulfides via an anionic thiolate-alkyne addition reaction was achieved when the terminal alkynes and benzyl mercaptans were reacted using tBuOLi (0.5 equiv) in EtOH under ambient conditions. Exclusive stereoselectivity (ca. 100%) was achieved by stereoelectronic control via anti-periplanar and anti-Markovnikov addition of benzylthiolates to phenylacetylenes. Solvolysis of lithium thiolate ion pairs in ethanol significantly suppresses the competing formation of the E-isomer. A remarkable enhancement of the Z-selectivity under a longer reaction time was observed.