Synthesis of 伪,尾-Unsaturated N-Aryl Ketonitrones from Oximes and Diaryliodonium Salts: Observation of a Metal-Free N-Arylation Process

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• 作者：Xiao-Pan Ma ; Wei-Min Shi ; Xue-Ling Mo ; Xiao-Hua Li ; Liang-Gui Li ; Cheng-Xue Pan ; Bo Chen ; Gui-Fa Su ; Dong-Liang Mo
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：October 16, 2015
• 年：2015
• 卷：80
• 期：20
• 页码：10098-10107
• 全文大小：540K
• ISSN：1520-6904

文摘

An efficient transition-metal-free method for the preparation of 伪,尾-unsaturated N-aryl ketonitrones under mild conditions has been developed. This reaction shows good functional group tolerance for both electron-rich and electron-deficient substituents on both oximes and diaryliodonium salts. Two examples of gram-scale preparations have been realized in good yields. Further transformations of these nitrones to different N-heterocycles have been demonstrated. DFT calculations suggest that N-arylation products are formed by [1,3]-phenyl migration of an O-coordinated oximate complex via a four-centered transition state, while the O-arylation products are formed by [1,3]-phenyl migration of a N-coordinated oximate complex.