Unexpected Role of p-Toluenesulfonylmethyl Isocyanide as a Sulfonylating Agent in Reactions with α-Bromocarbonyl Compounds

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• 作者：Jiajia Chen ; Wei Guo ; Zhenrong Wang ; Lin Hu ; Fan Chen ; Yuanzhi Xia
• 刊名：Journal of Organic Chemistry
• 出版年：2016
• 出版时间：July 1, 2016
• 年：2016
• 卷：81
• 期：13
• 页码：5504-5512
• 全文大小：506K
• 年卷期：0
• ISSN：1520-6904

文摘

The reactions of p-toluenesulfonylmethyl isocyanide (TosMIC) with α-bromocarbonyl compounds leading efficiently to α-sulfonated ketones, esters, and amides were reported, in which an explicit new role of TosMIC as the sulfonylating agent was uncovered for the first time. Mechanistic study by control experiments and DFT calculations suggested that the reaction is initiated by Cu(OTf)₂-catalyzed hydration of TosMIC to form a formamide intermediate, which undergoes facile C–S bond cleavage under the mediation of a Cs₂CO₃ additive.