Li Long-Hai, Gu Xin-Tao, Shi Min, Wei Yin
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
Chem Sci. 2022 Oct 12;13(43):12851-12857. doi: 10.1039/d2sc03385b. eCollection 2022 Nov 9.
The amination and alkenylation of the C(sp)-H bond at the -α position of secondary benzamides were both realized in this work by using -hydroxyphthalimide (NHPI) imidate esters as substrates under a dual catalysis involving a photoredox catalyst and hydrogen atom transfer (HAT) catalyst. The developed methods significantly extended the scope of applications of the -α position C(sp)-H bond functionalization with regard to secondary -alkylamides. More importantly, new reaction models in photoredox catalysis have been established. Based on corresponding experiments and density functional theory (DFT) calculations on the critical reaction steps combined with information reported previously, we proposed a synergistic photo- and organocatalytic reaction process for the C(sp)-H bond functionalization and also clarified the occurrence of a chain process in the reaction pathway.
在这项工作中，通过使用邻羟基苯二甲酰亚胺（NHPI）亚胺酯作为底物，在光氧化还原催化剂和氢原子转移（HAT）催化剂的双催化作用下，实现了仲苯甲酰胺α位C(sp) -H键的胺化和烯基化反应。所开发的方法显著扩展了仲烷基酰胺α位C(sp) -H键官能化的应用范围。更重要的是，建立了光氧化还原催化中的新反应模型。基于相应的实验以及对关键反应步骤的密度泛函理论（DFT）计算，并结合先前报道的信息，我们提出了一种用于C(sp) -H键官能化的光催化与有机催化协同反应过程，同时阐明了反应途径中链反应过程的发生情况。
