Wu Shuo, Wu Xinxin, Wang Dongping, Zhu Chen
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering, and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu, 215123, China.
Angew Chem Int Ed Engl. 2019 Jan 28;58(5):1499-1503. doi: 10.1002/anie.201812927. Epub 2018 Dec 28.
Regioselective incorporation of a particular functional group into aliphatic sites by direct activation of unreactive C-H bonds is of great synthetic value. Despite advances in radical-mediated functionalization of C(sp )-H bonds by a hydrogen-atom transfer process, the site-selective vinylation of remote C(sp )-H bonds still remains underexplored. Reported herein is a new protocol for the regioselective vinylation of unactivated C(sp )-H bonds. The remote C(sp )-H activation is promoted by a C-centered radical instead of the commonly used N and O radicals. The reaction possesses high product diversity and synthetic efficiency, furnishing a plethora of synthetically valuable E alkenes bearing tri-/di-/mono-fluoromethyl and perfluoroalkyl groups.
通过直接活化惰性C-H键将特定官能团区域选择性引入脂肪族位点具有重大的合成价值。尽管通过氢原子转移过程实现了C(sp³)-H键的自由基介导官能团化取得了进展，但远程C(sp³)-H键的位点选择性乙烯基化仍未得到充分探索。本文报道了一种用于未活化C(sp³)-H键区域选择性乙烯基化的新方法。远程C(sp³)-H活化是由碳中心自由基促进的，而不是常用的氮和氧自由基。该反应具有高产物多样性和合成效率，可提供大量具有合成价值的带有三氟甲基/二氟甲基/单氟甲基和全氟烷基的E-烯烃。
