Carbene-Catalyzed Activation of Remote Nitrogen Atoms of (Benz)imidazole-Derived Aldimines for Enantioselective Synthesis of Heterocycles

作     者：Dr. Xing Yang Dr. Yongtao Xie Dr. Jun Xu Dr. Shichao Ren Bivas Mondal Dr. Liejin Zhou Prof. Dr. Weiyi Tian Dr. Xinglong Zhang Dr. Lin Hao Dr. Zhichao Jin Prof. Dr. Yonggui Robin Chi 

作者机构：Division of Chemistry & Mathematical Science School of Physical & Mathematical Sciences Nanyang Technological University Singapore 637371 Singapore International Joint Research Center for Molecular Science College of Chemistry and Environmental Engineering Shenzhen University Shenzhen 518060 China Guizhou University of Traditional Chinese Medicine Guiyang 550025 China Institute of High Performance Computing A*STAR (Agency for Science Technology and Research) Singapore 138632 Singapore Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering Key Laboratory of Green Pesticide and Agricultural Bioengineering Ministry of Education Guizhou University Huaxi District Guiyang 550025 China 

出 版 物：《Angewandte Chemie》 

年 卷 期：2021年第133卷第14期

学科分类：081704[工学-应用化学] 08[工学] 0817[工学-化学工程与技术] 

主　　题：imines heteroatom activation heterocycles triaza-diene N-heterocyclic carbene 

摘      要：A new mode of carbene-catalyzed heteroatom activation and asymmetric reactions is disclosed. The reaction starts with addition of a carbene catalyst to a (benz)imidazole-derived aldimine substrate. Subsequent oxidation and proton transfer lead to the formation of a catalyst-bound triaza-diene as the key intermediate, in which the nitrogen atom at a site remote to the catalyst-substrate bond is activated. This unusual triaza-diene intermediate then undergoes highly enantioselective reactions with activated ketones through a concerted asynchronous pathway, as supported by mechanistic studies and preliminary density function theory calculation.