Jiang Yuan-Xu, Chen Liang, Ran Chuan-Kun, Song Lei, Zhang Wei, Liao Li-Li, Yu Da-Gang
Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu, 610064, P. R. China.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University, School of Chemistry and Molecular Engineering, 3663N Zhongshan Road, Shanghai, 200062, P. R. China.
ChemSusChem. 2020 Dec 7;13(23):6312-6317. doi: 10.1002/cssc.202002032. Epub 2020 Oct 23.
The carboxylation of cyclic oxime esters with carbon dioxide via visible-light photoredox catalysis is demonstrated for the first time. A variety of cyclic oxime esters undergo ring-opening C-C bond cleavage and carboxylation to give cyanoalkyl-containing carboxylic acids in moderate to good yields. Moreover, this methodology features mild reaction conditions (room temperature, 1 atm), wide substrate scope, good functional group tolerance as well as facile derivations of products. Mechanistic studies indicate that the benzylic radicals and anions might be the key intermediates.
首次展示了通过可见光光氧化还原催化使环状肟酯与二氧化碳进行羧化反应。多种环状肟酯发生开环C-C键裂解和羧化反应，以中等至良好的产率得到含氰基烷基的羧酸。此外，该方法具有反应条件温和（室温，1个大气压）、底物范围广、官能团耐受性好以及产物易于衍生化等特点。机理研究表明，苄基自由基和阴离子可能是关键中间体。
