Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
Institute for Molecular Science, National Institutes of Natural Sciences, 5-1 Higashiyama Myodaiji, Okazaki, 444-8787, Japan.
Chemistry. 2018 Jun 7;24(32):8051-8055. doi: 10.1002/chem.201801746. Epub 2018 May 4.
Inspired by the reaction mechanism of photo-induced DNA cleavage in nature, a C(sp )-H cyanation reaction promoted by visible-light photoredox/phosphate hybrid catalysis was developed. Phosphate radicals, generated by one-electron photooxidation of phosphate salt, functioned as a hydrogen-atom-transfer catalyst to produce nucleophilic carbon radicals from C(sp )-H bonds with a high bond-dissociation energy. The resulting carbon radicals were trapped by a cyano radical source (TsCN) to produce the C-H cyanation products. Due to the high functional-group tolerance and versatility of the cyano group, the reaction will be useful for realizing streamlined building block syntheses and late-stage functionalization of drug-like molecules.
受自然中光诱导 DNA 断裂反应机制的启发，开发了一种可见光光氧化还原/磷酸盐协同催化促进的 C(sp )-H 氰化反应。磷酸盐自由基通过磷酸盐盐的单电子光氧化产生，作为氢原子转移催化剂，从具有高键离解能的 C(sp )-H 键中产生亲核碳自由基。所得的碳自由基被氰基自由基源（TsCN）捕获，生成 C-H 氰化产物。由于氰基的高官能团容忍性和通用性，该反应将有助于实现砌块的流畅合成和药物样分子的后期功能化。
