Kong Manman, Wang Zhuoxi, Ban Xu, Zhao Xiaowei, Yin Yanli, Zhang Junmin, Jiang Zhiyong
International Joint Research Center for Molecular Science, College of Chemistry and Environmental Engineering, College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen, 518060, P. R. China.
School of Chemistry and Chemical Engineering, Pingyuan Laboratory, Henan Normal University, Xinxiang, Henan, 453007, P. R. China.
Adv Sci (Weinh). 2024 Mar;11(12):e2307773. doi: 10.1002/advs.202307773. Epub 2024 Jan 17.
An unprecedented enantioselective protonation reaction enabled by photoredox catalytic radical coupling is developed. Under cooperative dicynopyrazine-derived chromophore (DPZ) as a photosensitizer and a chiral phosphoric acid catalyst, and Hantzsch ester as a sacrificial reductant, the transformations between α-substituted enones and cyanoazaarenes or 2-(chloromethyl)azaaren-1-iums can proceed a tandem reduction, radical coupling, and enantioselective protonation process efficiently. Two classes of pharmaceutically important enantioenriched azaarene variants, which contain a synthetically versatile ketone-substituted tertiary carbon stereocenter at the β- or γ-position of the azaarenes, are synthesized with high yields and ees.
开发了一种由光氧化还原催化自由基偶联实现的前所未有的对映选择性质子化反应。在双氰基吡嗪衍生的发色团（DPZ）作为光敏剂、手性磷酸催化剂以及汉斯酯作为牺牲还原剂的协同作用下，α-取代烯酮与氰基氮杂芳烃或2-（氯甲基）氮杂芳烃-1-鎓之间的转化能够高效地进行串联还原、自由基偶联和对映选择性质子化过程。两类在药学上重要的对映体富集氮杂芳烃变体被高收率和高对映体过量地合成出来，它们在氮杂芳烃的β-或γ-位含有一个具有合成多功能性的酮取代叔碳立体中心。
