Au-Catalyzed Oxidative Arylation: Chelation-Induced Turnover of <i>ortho</i>-Substituted Arylsilanes

Abstract

<i>ortho</i>-Substituted aryl silanes have previously been found to undergo much slower Au-catalyzed intermolecular arylation than their <i>m,p</i>-substituted isomers, with many examples failing to undergo turnover at all. A method to indirectly quantify the rates of C–Si auration of <i>o</i>-substituted aryl silanes, under conditions of turnover, has been developed. All examples are found to undergo very efficient C–Si auration, indicative that it is the subsequent C–H auration that is inhibited by the <i>ortho</i> substituent. A simple Ar–Au conformational model suggests that C–H auration can be accelerated by chelation. A series of <i>ortho</i>-functionalized aryl silanes are shown to undergo efficient arylation