Copper-Initiated Regiodivergent Chloropentafluorosulfanylation of 1,3-Enynes under Substrate Control.

A copper-catalyzed regiodivergent chloropentafluorosulfanylation strategy for 1,3-enynes using SFCl has been developed. The regioselectivity is dictated by the structural and substitution patterns of 1,3-enynes, enabling facile access to three classes of SF-containing products: propargylic chlorides, 1,3-dienes, and allenes. The reaction systems involve radical species, where the transfer of a chlorine atom from SFCl to a carbon radical is considered the predominant pathway. Diverse types of SF- building blocks can be synthesized through simple functional group transformations.