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Switching the site-selectivity of C-H activation in aryl sulfonamides containing strongly coordinating N-heterocycles.

Yi DongXuePeng ZhangJiajing ChenWenxing ZouSongwen LinHeng Xu
Published in: Chemical science (2019)
The limitations of arene C-H functionalization of aryl sulfonamides containing strongly coordinating N-heterocycles were overcome using a Rh(iii) catalyst. The site-selectivity of C-H carbenoid functionalization at the ortho position relative to either the sulfonamide or N-heterocycle directing groups was elegantly switched using solvents of different polarities and different additive concentrations. Importantly, sulfonamide-group-directed ortho-C-H carbenoid functionalization tolerated strongly coordinating N-heterocycles, including pyridine, pyrrole, thiazole, pyrimidine, and pyrazine. Density functional theory (DFT) calculations were performed to rationalize the reaction mechanisms and the influence of reaction polarity.
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