Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Corrensstrasse 40, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2018 Feb 5;57(6):1692-1696. doi: 10.1002/anie.201712066. Epub 2018 Jan 15.
A method for site-specific intermolecular γ-C(sp )-H functionalization of ketones has been developed using an α-aminoxy acid auxiliary applying photoredox catalysis. Regioselective activation of an inert C-H bond is achieved by 1,5-hydrogen atom abstraction by an oxidatively generated iminyl radical. Tertiary and secondary C-radicals thus formed at the γ-position of the imine functionality undergo radical conjugate addition to various Michael acceptors to provide, after reduction and imine hydrolysis, the corresponding γ-functionalized ketones.
开发了一种使用α-氨氧基酸辅助物通过光氧化还原催化实现酮的位点特异性γ-C(sp )-H 功能化的方法。通过氧化生成的亚胺基自由基的 1,5-氢原子消除来实现惰性 C-H 键的区域选择性活化。由此在亚胺官能团的γ-位形成的叔和仲 C-自由基经历自由基共轭加成到各种迈克尔受体，以在还原和亚胺水解后提供相应的γ-官能化酮。
