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.