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Iridium(III)‐Catalyzed Regioselective Intermolecular Unactivated Secondary Csp 3 −H Bond Amidation
Author(s) -
Xiao Xinsheng,
Hou Cheng,
Zhang Zhenhui,
Ke Zhuofeng,
Lan Jianyong,
Jiang Huanfeng,
Zeng Wei
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201606531
Subject(s) - regioselectivity , nitrene , iridium , chemistry , intermolecular force , density functional theory , catalysis , combinatorial chemistry , ligand (biochemistry) , computational chemistry , stereochemistry , organic chemistry , molecule , biochemistry , receptor
For the first time, a highly regioselective intermolecular sulfonylamidation unactivated secondary Csp 3 −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 Csp 3 −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 Csp 3 −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.