Selective Gram-Scale C-H Carbenoid Functionalization of N-Sulfonylarylamides with a Rhodium Catalyst
Yi Dong1,2, Bo Mei1,2, Xue-Peng Zhang3
1State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China.
Abstract:
This work describes an effective Cp*RhIII-catalyzed C-H carbenoid functionalization of N-sulfonylarylamides. Compared to the previous late-stage C-H modification methods of N-sulfonylarylamide analogues, this method efficiently achieves the gram-scale transformation with 2.5 mol % Rh-catalyst loading at 0 °C or with a 0.1 mol % Rh-catalyst loading at room temperature. The reaction medium has a great influence on the reaction rate. Methanol is optimal, and adding a nonpolar solvent (such as toluene or 1,2-dichloroethane) causes the rate to decrease. Experiments and density functional theory calculations were performed to rationalize the mechanism of rate control by a polar medium.
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