Nickel-catalysed enantioselective hydrosulfenation of alkynes

Enantioenriched sulfoxides have found ever-increasing applications in marketed drugs or as candidates in clinical trials. They are also frequently used as key motifs in chiral ligands or as organocatalysts in asymmetric catalysis. However, the asymmetric synthesis of such a functionality poses a significant challenge. Here, by harnessing the strong backbonding donation of Ni(0) to alkynes, we report a Ni-catalysed hydrosulfenation reaction of unactivated alkynes with in situ-generated sulfenic acids, enabling the reaction to proceed in an enantioselective stepwise mechanism that is contrary to the well-established uncatalysed concerted mechanism. A plethora of alkenyl sulfoxides were synthesized with high enantioselectivity and a broad substrate scope. The products could be easily elaborated into structurally diverse sulfoxides that could serve as chiral ligands, catalysts and useful pharmacophores for the late-stage modification of drugs.