Candish L, Freitag M, Gensch T, Glorius F
Organisch-Chemisches Institut , Westfälische Wilhelms-Universität Münster , Corrensstrasse 40 , 48149 , Münster , Germany . Email:
Chem Sci. 2017 May 1;8(5):3618-3622. doi: 10.1039/c6sc05533h. Epub 2017 Feb 27.
Herein we present the first example of aryl radical formation the visible light-mediated decarboxylation of aryl carboxylic acids using photoredox catalysis. This method constitutes a mild protocol for the decarboxylation of cheap and abundant aryl carboxylic acids and tolerates both electron-rich substrates and those lacking -substitution. The formation of an acyl hypobromite is proposed to prevent unproductive hydrogen atom abstraction and trapping of the intermediate aroyloxy radical, enabling mild decarboxylation.
在此,我们展示了芳基自由基形成的首个实例——使用光氧化还原催化实现芳基羧酸的可见光介导脱羧反应。该方法为廉价且丰富的芳基羧酸脱羧提供了一种温和的方案,并且耐受富电子底物以及缺乏α-取代的底物。有人提出,酰基次溴酸盐的形成可防止无效的氢原子夺取以及中间体芳酰氧基自由基的捕获,从而实现温和脱羧。