Kangkui Li, Yue Huang, Xianyang Long, Dong Zhu, Chen Yang, Shifa Zhu
The stereoselective synthesis of cis -vinyl iodides represents a long-standing challenge in organic synthesis, with Stork–Zhao olefination remaining the benchmark methodology since its inception in 1989. Herein, we report a synergistic photoredox/nickel dual-catalytic system that enables the efficient cis -carboniodination of acetylene, affording cis -vinyl iodides with exceptional selectivity and 100% atom economy. Mechanistic studies reveal that the cis -insertion of an aryl-nickel intermediate into acetylene is pivotal for stereocontrol, while photoexcitation of the redox catalyst facilitates the generation of transient vinyl-Ni(III) species, thereby promoting reductive elimination to form the C–I bond with high fidelity. Furthermore, this protocol is extendable to the synthesis of vinyl ethers via tandem C–O coupling when alcohols are introduced into the reaction system. This operationally simple yet mechanistically sophisticated strategy not only offers a sustainable and atom-economical approach to cis -vinyl iodides and ethers but also establishes a versatile platform for the difunctionalization of acetylene under mild conditions.