Pan Shiwei, Chen Fan, Zhang Yanyan, Shao Liang, Chu Lingling
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry and Chemical Engineering, Center for Advanced Low-dimension Materials, Donghua University, Shanghai, 201620, China.
Angew Chem Int Ed Engl. 2023 Aug 1;62(31):e202305426. doi: 10.1002/anie.202305426. Epub 2023 Jun 26.
A Markovnikov-selective hydrodifluoromethylation of alkynes with BrCF H via nickel catalysis is described. This protocol proceeds via a migratory insertion of nickel hydride to alkyne followed by a CF H-coupling, enabling straightforward access to diverse branched CF H-alkenes with high efficiency and exclusive regioselectivity. The mild condition applies to a wide array of aliphatic and aryl alkynes with good functional group compatibility. Mechanistic studies are presented to support the proposed pathway.
描述了一种通过镍催化使炔烃与BrCF₂H进行马氏选择性氢二氟甲基化反应。该反应通过氢化镍向炔烃的迁移插入，随后进行CF₂H偶联来进行，能够高效且具有专一区域选择性地直接获得各种支链CF₂H-烯烃。温和的反应条件适用于多种具有良好官能团兼容性的脂肪族和芳基炔烃。文中还给出了机理研究以支持所提出的反应途径。
