Wang Qian, Ni Chuanfa, Hu Mingyou, Xie Qiqiang, Liu Qinghe, Pan Shitao, Hu Jinbo
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2020 May 25;59(22):8507-8511. doi: 10.1002/anie.202002409. Epub 2020 Mar 19.
A Cu-catalyzed gem-bis(trifluoromethyl)olefination of α-diazo esters, using TMSCF as the only fluorocarbon source, has been developed and provides an exquisite method to access gem-bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into "CuCF " to generate the α-CF -substituted organocopper species, which then undergoes β-fluoride elimination and two consecutive addition-elimination processes to give the desired products. The key to this efficient one-pot C -to-C synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem-difluoroalkene intermediates.
已开发出一种以TMSCF作为唯一碳氟化合物源的铜催化α-重氮酯的偕二（三氟甲基）烯烃化反应，该反应为制备偕二（三氟甲基）烯烃提供了一种精妙的方法。这一前所未有的烯烃化过程涉及卡宾迁移插入到“CuCF”中以生成α-CF-取代的有机铜物种，然后该物种经历β-氟消除以及两个连续的加成-消除过程以得到所需产物。这种高效的一锅法碳-碳合成方案的关键在于偕二氟烯烃中间体可控的双（相对于单和三）三氟甲基化。
