State Key Lab of Urban Water Resource and Environment, School of Science, Harbin Institute of Technology (Shenzhen), Shenzhen 518055, China.
School of Mechatronics Engineering, Harbin Institute of Technology, Harbin 150001, China.
Org Lett. 2022 Sep 16;24(36):6560-6565. doi: 10.1021/acs.orglett.2c02523. Epub 2022 Sep 7.
We report a vinyl radical-mediated 1,5-hydrogen atom transfer (1,5-HAT) strategy for the remote C(sp)-H functionalization reaction, which includes cyanation, oxidation, and etherification under visible-light-induced photochemical conditions. This reaction is achieved using readily available alkyl -hydroxyphthalimide esters as radical precursors, which can efficiently react with diverse alkynes to form key vinyl radical intermediates followed by a 1,5-HAT process. A series of structurally diverse γ-cyano, γ-carbonyl, and γ-oxygenated alkenes with excellent stereoselectivity can be efficiently constructed by this synthetic protocol.
我们报告了一种乙烯基自由基介导的 1,5-氢原子转移（1,5-HAT）策略，用于远程 C(sp)-H 功能化反应，该反应包括在可见光诱导光化学条件下的氰化、氧化和醚化。该反应使用易得的烷基 -羟基邻苯二甲酰亚胺酯作为自由基前体来实现，可以有效地与各种炔烃反应，形成关键的乙烯基自由基中间体，然后进行 1,5-HAT 过程。通过这个合成方案，可以有效地构建一系列结构多样的γ-氰基、γ-羰基和γ-氧代烯烃，具有优异的立体选择性。
