State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry, Chemical Engineering and Biotechnology, Center for Advanced Low-Dimension Materials, Donghua University, Shanghai, 201620, China.
Nat Commun. 2018 Oct 31;9(1):4543. doi: 10.1038/s41467-018-06904-9.
Substituted alkenes are pivotal structural motifs found in pharmaceuticals and agrochemicals. Although numerous methods have been developed to construct substituted alkenes, a generally efficient, mild, catalytic platform for the conversion of alkynes to this highly functionalized scaffold via successive C-C bond forming steps remains in high demand. Here we describe an intermolecular, regio- and syn-stereoselective alkylarylation of terminal alkynes with tertiary alkyl oxalates via photoredox-Ni dual catalysis. This catalytic protocol, synergistically combining Ir/Ni-catalyzed alkyne difunctionalization with photoinduced alkene isomerization, affords trisubstituted alkenes with excellent efficiency and syn-stereoselectivity. The mild conditions tolerate many functional groups, allowing for a broad scope with respect to terminal alkynes, aryl bromides, and alkyl oxalates.
取代的烯烃是药物和农用化学品中重要的结构基序。虽然已经开发出许多方法来构建取代的烯烃，但通过连续的 C-C 键形成步骤将炔烃转化为这种高官能化支架的通用、温和、催化平台仍然有很高的需求。在这里，我们描述了通过光还原-Ni 双重催化，末端炔烃与叔烷基丙二酸酯的分子间、区域和 syn-立体选择性的烷基芳基化反应。这种催化方案协同结合了 Ir/Ni 催化的炔烃双官能化和光诱导烯烃异构化，以优异的效率和 syn-立体选择性提供了三取代烯烃。温和的条件可以耐受许多官能团，因此对于末端炔烃、芳基溴化物和丙二酸酯，具有广泛的适用范围。
