Iridium(III)-Catalyzed Regioselective Intermolecular Unactivated Secondary Csp³−H Bond Amidation

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• 作者：Dr. Xinsheng Xiao ; Dr. Cheng Hou ; Zhenhui Zhang ; Prof. Zhuofeng Ke ; Jianyong Lan ; Prof. Huanfeng Jiang and Prof. Wei Zeng
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：September 19, 2016
• 年：2016
• 卷：55
• 期：39
• 页码：11897-11901
• 全文大小：853K
• ISSN：1521-3773

文摘

For the first time, a highly regioselective intermolecular sulfonylamidation unactivated secondary Csp³−H bond has been achieved using Ir^III catalysts. The introduced N,N’-bichelating ligand plays a crucial role in enabling iridium–nitrene insertion into a secondary Csp³−H bond via an outer-sphere pathway. Mechanistic studies and density functional theory (DFT) calculations demonstrated that a two-electron concerted nitrene insertion was involved in this Csp³−H amidation process. This method tolerates a broad range of linear and branched-chain N-alkylamides, and provides efficient access to diverse γ-sulfonamido-substituted aliphatic amines.