title: Copper-Catalyzed Radical/Radical C(sp 3)-H/P-H Cross-Coupling: α-Phosphorylation of Aryl Ketone O-Acetyloximes.
abstract: The selective radical/radical cross-coupling of two different organic radicals is a great challenge due to the inherent activity of radicals. In this paper, a copper-catalyzed radical/radical C(sp 3)-H/P-H cross-coupling has been developed. It provides a radical/radical cross-coupling in a selective manner. This work offers a simple way toward β-ketophosphonates by oxidative coupling of aryl ketone o-acetyloximes with phosphine oxides using CuCl as catalyst and PCy3 as ligand in dioxane under N2 atmosphere at 130 °C for 5 h, and yields ranging from 47% to 86%. The preliminary mechanistic studies by electron paramagnetic resonance (EPR) showed that, 1) the reduction of ketone o-acetyloximes generates iminium radicals, which could isomerize to α-sp(3) -carbon radical species; 2) phosphorus radicals were generated from the oxidation of phosphine oxides. Various aryl ketone o-acetyloximes and phosphine oxides were suitable for this transformation.
authors: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072 (P.R. China) http://aiwenlei.whu.edu.cn/Main_Website/
authors: Jie
authors: J
authors: Ke
authors: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072 (P.R. China) http://aiwenlei.whu.edu.cn/Main_Website/
authors: Yuliang
authors: Y
authors: Tang
authors: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072 (P.R. China) http://aiwenlei.whu.edu.cn/Main_Website/
authors: Hong
authors: H
authors: Yi
authors: Key Laboratory for Organic Electronics and Information Display and Institute of Advanced Materials, Nanjing University of Posts and Telecommunications, Nanjing, 210023 (P.R. China).
authors: Yali
authors: Y
authors: Li
authors: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072 (P.R. China) http://aiwenlei.whu.edu.cn/Main_Website/
authors: Yongde
authors: Y
authors: Cheng
authors: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072 (P.R. China) http://aiwenlei.whu.edu.cn/Main_Website/
authors: Chao
authors: C
authors: Liu
authors: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072 (P.R. China) http://aiwenlei.whu.edu.cn/Main_Website/. aiwenlei@whu.edu.cn.|State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, 730000 Lanzhou (P.R. China). aiwenlei@whu.edu.cn.
authors: Aiwen
authors: A
authors: Lei
keywords: C(sp3)P bonds; copper catalysis; oxidative coupling; radical/radical cross-coupling; β-ketophosphonates