Li Guo-Xing, Morales-Rivera Christian A, Wang Yaxin, Gao Fang, He Gang, Liu Peng, Chen Gong
State Key Laboratory and Institute of Elemento-Organic Chemistry , Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Nankai University , Tianjin 300071 , China . Email:
Department of Chemistry , University of Pittsburgh , Pittsburgh , PA 15260 , USA . Email:
Chem Sci. 2016 Oct 1;7(10):6407-6412. doi: 10.1039/c6sc02653b. Epub 2016 Jul 12.
A photoredox-mediated Minisci C-H alkylation reaction of -heteroarenes with alkyl boronic acids is reported. A broad range of primary and secondary alkyl groups can be efficiently incorporated into various -heteroarenes using [Ru(bpy)]Cl as photocatalyst and acetoxybenziodoxole as oxidant under mild conditions. The reaction exhibits excellent substrate scope and functional group tolerance, and offers a broadly applicable method for late-stage functionalization of complex substrates. Mechanistic experiments and computational studies suggest that an intramolecularly stabilized -iodobenzoyloxy radical intermediate might play a key role in this reaction system.
报道了一种光氧化还原介导的杂芳烃与烷基硼酸的Minisci C-H烷基化反应。在温和条件下，以[Ru(bpy)]Cl为光催化剂、乙酰氧基苯碘酰为氧化剂，可将多种伯烷基和仲烷基高效引入到各种杂芳烃中。该反应具有优异的底物范围和官能团耐受性，为复杂底物的后期官能团化提供了一种广泛适用的方法。机理实验和计算研究表明，分子内稳定的碘苯甲酰氧基自由基中间体可能在该反应体系中起关键作用。
