Ren Xinyi, Shen Chaoren, Wang Guangzhu, Shi Zhanglin, Tian Xinxin, Dong Kaiwu
Chang-Kung Chuang Institute, and Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, P. R. China.
Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University, Taiyuan 030006, P. R. China.
Org Lett. 2021 Apr 2;23(7):2527-2532. doi: 10.1021/acs.orglett.1c00465. Epub 2021 Mar 24.
Reductive cyanation of tertiary alkyl bromides using electrophilic cyanating reagent and zinc reductant was developed, providing various α-cyano ketones, esters, and carboxamides containing a nitrile-bearing all-carbon quaternary center in good to excellent yields under mild reaction conditions. The corresponding reaction mechanism involving in situ generated organozinc reagent and reactivity distinction was elucidated by density functional theory computation.
开发了使用亲电氰化试剂和锌还原剂对叔烷基溴进行还原氰化反应的方法，该方法能在温和的反应条件下，以良好至优异的产率提供各种含有腈基全碳季碳中心的α-氰基酮、酯和羧酰胺。通过密度泛函理论计算阐明了涉及原位生成有机锌试剂的相应反应机理及反应活性差异。
