Scalable Rhodium(III)‐Catalyzed Aryl C−H Phosphorylation Enabled by Anodic Oxidation Induced Reductive Elimination

作者：Zheng‐Jian Wu, Feng Su, Weidong Lin, Jinshuai Song, Ting‐Bin Wen, Hui‐Jun Zhang, Hai‐Chao Xu · 发表于：Angewandte Chemie International Edition · 年份：2019 · DOI：10.1002/anie.201909951 · 被引用次数：149 · 研究领域：Catalytic C–H Functionalization Methods、Asymmetric Hydrogenation and Catalysis、Radical Photochemical Reactions

Abstract Transition metal catalyzed C−H phosphorylation remains an unsolved challenge. Reported methods are generally limited in scope and require stoichiometric silver salts as oxidants. Reported here is an electrochemically driven Rh III ‐catalyzed aryl C−H phosphorylation reaction that proceeds through H 2 evolution, obviating the need for stoichiometric metal oxidants. The method is compatible with a variety of aryl C−H and P−H coupling partners and particularly useful for synthesizing triarylphosphine oxides from diarylphosphine oxides, which are often difficult coupling partners for transition metal catalyzed C−H phosphorylation reactions. Experimental results suggest that the mechanism responsible for the C−P bond formation involves an oxidation‐induced reductive elimination process.