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.
Key Laboratory of Synthesis Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry , Chinese Academy of Science , 345 Lingling Road , Shanghai 200032 , China.
Org Lett. 2019 Feb 1;21(3):821-825. doi: 10.1021/acs.orglett.8b04104. Epub 2019 Jan 17.
A new approach for generation of alkoxy radical from the O-H bond of cyanohydrin promoted by visible-light photoredox catalysis is reported. The alkoxy radical triggers the successive remote HAT and intramolecular cyano migration, leading to the regioselective cyanation of remote C(sp)-H bonds. The reaction exhibits a broad functional group tolerance that allows many sensitive groups to remain intact under mild conditions. To demonstrate the utility of method, the ketonitrile products are converted to other synthetically valuable compounds.
本文报道了可见光光氧化还原催化促进氰醇的 O-H 键生成烷氧基自由基的新方法。烷氧基自由基引发远程 HAT 和分子内氰基迁移反应，实现了区域选择性的远程 C(sp3)-H 键氰化反应。该反应具有广泛的官能团容忍性，在温和条件下许多敏感基团都能保持完整。为了证明该方法的实用性，酮腈产物可转化为其他具有合成价值的化合物。
