Lv Daqi, Sun Qiao, Zhou Huan, Ge Liang, Qu Yanjie, Li Taian, Ma Xiaoxu, Li Yajun, Bao Hongli
Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian, 350002, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Angew Chem Int Ed Engl. 2021 May 25;60(22):12455-12460. doi: 10.1002/anie.202017175. Epub 2021 Apr 28.
Asymmetric aminoazidation and diazidation of alkenes are straightforward strategies to build value-added chiral nitrogen-containing compounds from feedstock chemicals. They provide direct access to chiral organoazides and complement enantioselective diamination. Despite the advances in non-asymmetric reactions, asymmetric aminoazidation or diazidation based on acyclic systems has not been previously reported. Here we describe the iron-catalyzed intermolecular asymmetric aminoazidation and diazidation of styrenes. The method is practically useful and requires relatively low loading of catalyst and chiral ligand. With mild reaction conditions, the reaction can be completed on a 20 mmol scale. Studies of the mechanism suggest that the reaction proceeds via a radical pathway and involves stereocontrol of an acyclic free radical which probably takes place through a group transfer mechanism.
烯烃的不对称氨基叠氮化和双叠氮化反应是从基础化学品构建增值手性含氮化合物的直接策略。它们提供了直接合成手性有机叠氮化物的方法，并补充了对映选择性双胺化反应。尽管非不对称反应取得了进展，但基于开环体系的不对称氨基叠氮化或双叠氮化反应此前尚未见报道。在此，我们描述了铁催化的苯乙烯分子间不对称氨基叠氮化和双叠氮化反应。该方法具有实际应用价值，且所需催化剂和手性配体的负载量相对较低。在温和的反应条件下，该反应可以在20 mmol规模上完成。机理研究表明，该反应通过自由基途径进行，涉及对开环自由基的立体控制，这可能是通过基团转移机制实现的。
