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.

对映体富集的亚砜在市售药物或临床试验候选药物中的应用越来越多。它们还经常用作手性配体中的关键基序或不对称催化中的有机催化剂。然而，这种功能的不对称合成提出了重大挑战。在这里，通过利用 Ni(0) 对炔烃的强背键捐赠，我们报道了未活化炔烃与原位生成的次磺酸的 Ni 催化氢硫化反应，使反应能够以对映选择性逐步机制进行，这与完善的非催化协同机制。合成了大量具有高对映选择性和广泛底物范围的烯基亚砜。