Syn-Selective Chlorosulfonylation of Alkynes via a Copper-Powder-Initiated Atom Transfer Radical Addition Reaction and Mechanistic Studies

Copper-powder-catalyzed syn-selective chlorosulfonylation of readily available alkynes by an atom transfer radical addition (ATAR) process has been developed, providing straightforward access to a broad range of (Z)-β-chlorovinylsulfones in good yields under mild conditions. In addition, this method is ligand-free and features excellent stereoselectivity and high atom economy. Moreover, the product was obtained without an apparent loss of yield when the reaction was performed on the gram scale at a low catalyst loading. In this reaction, the copper powder not only acts as a sulfone radical initiator but also produces the catalytically active CuCl species. Mechanistic investigations and DFT calculation studies revealed that the stereoselectivity is controlled by the thermodynamic stabilities of the in situ-generated cyclic alkenyl CuII complex intermediate, which can serve as a chlorine atom transfer agent.