Singh Jatinder, Jones Spencer A, Nelson Tanner J, Botello Jesus A, Castle Steven L
Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, United States.
J Org Chem. 2023 Jul 21;88(14):10287-10297. doi: 10.1021/acs.joc.3c00915. Epub 2023 Jun 30.
Microwave irradiation of -phenyloximes triggers N-O homolysis and 1,5-hydrogen atom transfer (HAT), resulting in formal γ-C-H functionalization of ketones after trapping of the radical intermediate and imine hydrolysis. The Lewis acid InCl·HO facilitated HAT, enabling functionalization of benzylic and nonbenzylic secondary carbon atoms. Functionalization of primary carbons was feasible but afforded low yields, requiring ClCHCOH instead of InCl·HO as an additive. C-O and C-C bond formation could both be accomplished by this method.
对苯肟进行微波辐射会引发N-O均裂和1,5-氢原子转移（HAT），在捕获自由基中间体并进行亚胺水解后，实现酮的形式上的γ-C-H官能化。路易斯酸InCl·HO促进了氢原子转移，使得苄基和非苄基仲碳原子能够实现官能化。伯碳原子的官能化是可行的，但产率较低，需要使用ClCH₂CO₂H而不是InCl·HO作为添加剂。通过这种方法可以同时实现C-O键和C-C键的形成。
