Tan Zhenda, Fu Zhongxin, Yang Jian, Wu Yang, Cao Liang, Jiang Huanfeng, Li Juan, Zhang Min
Key Lab of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong, China.
Department of Chemistry, Jinan University, Huangpu Road West 601, Guangzhou, Guangdong 510632, P. R. China.
iScience. 2020 Apr 24;23(4):101003. doi: 10.1016/j.isci.2020.101003. Epub 2020 Mar 21.
Selective linkage of renewable alcohols and ammonia into functional products would not only eliminate the prepreparation steps to generate active amino agents but also help in the conservation of our finite fossil carbon resources and contribute to the reduction of CO emission. Herein the development of a novel 2-(4-methoxyphenyl)-1,8-naphthyridine-based iridium (III) complex is reported, which exhibits excellent catalytic performance toward a new hydrogen transfer-mediated annulation reaction of 2-nitrobenzylic alcohols with alcohols and ammonia. The catalytic transformation proceeds with the striking features of good substrate and functional group compatibility, high step and atom efficiency, no need for additional reductants, and liberation of HO as the sole by-product, which endows a new platform for direct access to valuable quinazolines. Mechanistic investigations suggest that the non-coordinated N-atom in the ligand serves as a side arm to significantly promote the condensation process by hydrogen bonding.
将可再生醇类与氨选择性地连接成功能产品，不仅可以省去生成活性氨基试剂的预制备步骤，还有助于保护我们有限的化石碳资源，并有助于减少一氧化碳排放。本文报道了一种新型的基于2-(4-甲氧基苯基)-1,8-萘啶的铱(III)配合物的开发，该配合物对2-硝基苄醇与醇类和氨的新型氢转移介导的环化反应表现出优异的催化性能。催化转化具有底物和官能团兼容性好、步骤和原子效率高、无需额外还原剂以及仅以水作为唯一副产物释放等显著特点，这为直接获得有价值的喹唑啉提供了一个新平台。机理研究表明，配体中未配位的氮原子作为侧链，通过氢键显著促进缩合过程。
