Iridium(III)-Catalyzed Direct Arylation of C鈥揌 Bonds with Diaryliodonium Salts

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• 作者：Pan Gao ; Wei Guo ; Jingjing Xue ; Yue Zhao ; Yu Yuan ; Yuanzhi Xia ; Zhuangzhi Shi
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：September 30, 2015
• 年：2015
• 卷：137
• 期：38
• 页码：12231-12240
• 全文大小：759K
• ISSN：1520-5126

文摘

By developing a new Ir(III)-catalyzed C鈥揅 cross-coupling, a versatile method for direct arylation of sp² and sp³ C鈥揌 bonds in ketoximes, nitrogen-containing heterocycles, various arenes, and olefins has been established. The key to this arylation depends on the appropriate choice of catalyst and the use of diaryliodonium triflate salts as the coupling partners. This transformation has good functional group compatibility and can serve as a powerful synthetic tool for late-stage C鈥揌 arylation of complex compounds. Mechanistic studies by density functional theory calculations suggested that the sp³ C鈥揌 activation was realized by a triflate-involved concerted metalation鈥揹eprotonation process, and the following oxidation of Ir(III) to Ir(V) is the most favorable when a bistriflimide is contained in the diaryliodonium salt. Calculations indicated that both steps are enabled by initial anion exchange between the reactant complexes.