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无金属手性共价有机框架的可见光介导水相选择性光氧化合成。

Synthesis of Metal-Free Chiral Covalent Organic Framework for Visible-Light-Mediated Enantioselective Photooxidation in Water.

机构信息

College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan 250014, PR China.

出版信息

J Am Chem Soc. 2022 Apr 20;144(15):6681-6686. doi: 10.1021/jacs.2c01186. Epub 2022 Apr 8.

Abstract

Although chiral covalent organic frameworks (CCOFs) presence grows in thermal asymmetric catalysis, their application in equally important asymmetric photocatalysis has yet to begin. Herein, we first report a propargylamine-linked and quaternary ammonium bromide decorated porphyrin-CCOF which can highly promote visible-light-driven enantioselective photooxidation of sulfides to sulfoxides in water and in air. This methodology has also been applied to the synthesis of ()-modafinil, a wakefulness-promoting medication used for the treatment of excessive sleepiness. This research might open a new way for the application of CCOFs in asymmetric photocatalysis.

摘要

尽管手性共价有机框架(CCOFs)在热不对称催化中得到了广泛应用,但它们在同样重要的不对称光催化中的应用尚未开始。在此,我们首次报道了一种炔丙胺连接的和季铵溴化物修饰的卟啉-CCOF,它可以在水中和空气中高度促进可见光驱动的对映选择性光氧化硫化物为亚砜。该方法还已应用于()-莫达非尼的合成,()-莫达非尼是一种用于治疗过度嗜睡的促醒药物。这项研究可能为 CCOFs 在不对称光催化中的应用开辟新途径。

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