Phosphine-Catalyzed Carbon-Sulfur Bond Formation

Significance

The authors report the phosphine-catalyzed asymmetric construction of carbon-­sulfur bonds, thus giving rise to γ-thioesters. The active catalyst, bisphosphine TangPhos 1, provides an array of products in high yields and good to excellent enantioselectivities. Among others, alkenes, alkynes, esters, acetals, and halides were well tolerated as allenoate substituents, while thiols with benzylic aromatic and heteroaromatic groups, as well as aliphatic and silylated functionalities were suitable nucleophiles.