Du Yi-Dan, Zhou Cong-Ying, To Wai-Pong, Wang Hai-Xu, Che Chi-Ming
State Key Laboratory of Synthetic Chemistry, Department of Chemistry, The University of Hong Kong China
Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry 354 Feng Lin Road Shanghai China.
Chem Sci. 2020 Apr 17;11(18):4680-4686. doi: 10.1039/d0sc00784f.
Visible light driven nitrene transfer and insertion reactions of organic azides are an attractive strategy for the design of C-N bond formation reactions under mild reaction conditions, the challenge being lack of selectivity as a free nitrene reactive intermediate is usually involved. Herein is described an iron(iii) porphyrin catalysed sp C-H amination and alkene aziridination with selectivity by using organic azides as the nitrogen source under blue LED light (469 nm) irradiation. The photochemical reactions display chemo- and regio-selectivity and are effective for the late-stage functionalization of natural and bioactive compounds with complexity. Mechanistic studies revealed that iron porphyrin plays a dual role as a photosensitizer and as a catalyst giving rise to a reactive iron-nitrene intermediate for subsequent C-N bond formation.
可见光驱动的有机叠氮化物的氮宾转移和插入反应是在温和反应条件下设计碳氮键形成反应的一种有吸引力的策略，挑战在于通常涉及游离氮宾反应中间体，缺乏选择性。本文描述了一种铁（III）卟啉催化的sp C-H胺化反应和烯烃氮杂环丙烷化反应，该反应在蓝色发光二极管（469 nm）光照下以有机叠氮化物为氮源，具有选择性。光化学反应表现出化学选择性和区域选择性，对于结构复杂的天然和生物活性化合物的后期官能团化是有效的。机理研究表明，铁卟啉作为光敏剂和催化剂发挥双重作用，产生反应性铁氮宾中间体用于后续的碳氮键形成。
Zotero 插件
