Zhao Huaibo, Leonori Daniele
Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Angew Chem Int Ed Engl. 2021 Mar 29;60(14):7669-7674. doi: 10.1002/anie.202100051. Epub 2021 Mar 3.
Anilines are some of the most used class of substrates for application in photoinduced electron transfer. N,N-Dialkyl-derivatives enable radical generation α to the N-atom by oxidation followed by deprotonation. This approach is however elusive to monosubstituted anilines owing to fast back-electron transfer (BET). Here we demonstrate that BET can be minimised by using photoredox catalysis in the presence of an exogenous alkylamine. This approach synergistically aids aniline SET oxidation and then accelerates the following deprotonation. In this way, the generation of α-anilinoalkyl radicals is now possible and these species can be used in a general sense to achieve divergent sp C-H functionalization.
苯胺是光致电子转移应用中最常用的一类底物。N,N-二烷基衍生物可通过氧化然后去质子化在氮原子的α位产生自由基。然而，由于快速的反向电子转移（BET），这种方法对于单取代苯胺来说难以实现。在这里，我们证明了在存在外源烷基胺的情况下使用光氧化还原催化可以将BET最小化。这种方法协同辅助苯胺单电子转移氧化，然后加速随后的去质子化。通过这种方式，现在可以生成α-苯胺基烷基自由基，并且这些物种通常可用于实现不同的sp C-H官能化。
