Tu Jia-Lin, Tang Wan, Xu Wei, Liu Feng
Jiangsu Key Laboratory of Neuropsychiatric Diseases and Department of Medicinal Chemistry, College of Pharmaceutical Sciences, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123, People's Republic of China.
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China.
J Org Chem. 2021 Feb 5;86(3):2929-2940. doi: 10.1021/acs.joc.0c02834. Epub 2021 Jan 22.
We report herein an unprecedented protocol for radical-olefin coupling of α-imino-oxy acids and alkenes for the synthesis of alkene-containing nitriles via synergistic photoredox and cobaloxime catalysis. With visible-light irradiation, the transformation provides a variety of corresponding alkene-containing nitriles under mild reaction conditions. The C-C bond cleavage/Heck-like coupling reaction could generate -selective coupling products with excellent chemo- and stereo-selectivity. This iminyl-radical-mediated reaction is external-oxidant-free, exhibits wide functional-group compatibility, and occurs with the extrusion of acetone, H, and CO.
我们在此报告了一种前所未有的协议，用于通过协同光氧化还原和钴肟催化，实现α-亚氨基氧基酸与烯烃的自由基-烯烃偶联反应，以合成含烯烃的腈类化合物。在可见光照射下，该转化反应在温和的反应条件下提供了多种相应的含烯烃腈类化合物。碳-碳键裂解/类Heck偶联反应能够生成具有优异化学和立体选择性的选择性偶联产物。这种亚胺基自由基介导的反应无需外部氧化剂，具有广泛的官能团兼容性，并且在丙酮、氢气和一氧化碳的脱出过程中发生。
