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炔烃与草酸盐的光催化氘代羧基化反应

Photocatalytic deuterocarboxylation of alkynes with oxalate.

作者信息

Xu Pei, Jiang Hao-Qiang, Xu Hui, Wang Sai, Jiang Hui-Xian, Zhu Song-Lei, Yin Long, Guo Dong, Zhu Xu

机构信息

Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University 209 Tongshan Road Xuzhou 221004 China

出版信息

Chem Sci. 2024 Jul 15;15(32):13041-13048. doi: 10.1039/d4sc03586k. eCollection 2024 Aug 14.

Abstract

Herein, a catalytic photoredox-neutral strategy for alkyne deuterocarboxylation with tetrabutylammonium oxalate as the carbonyl source and DO as the deuteration agent was described. For the first time, the oxalic salt acted as both the reductant and carbonyl source through single electron transfer and subsequential homolysis of the C-C bond. The strongly reductive CO radical anion species generated from oxalate played significant roles in realizing the global deuterocarboxylation of terminal and internal alkynes to access various tetra- and tri-deuterated aryl propionic acids with high yields and deuteration ratios.

摘要

在此,描述了一种催化光氧化还原中性策略,该策略以草酸四丁铵作为羰基源,以DO作为氘代试剂进行炔烃的氘代羧基化反应。草酸盐首次通过单电子转移和随后的C-C键均裂同时作为还原剂和羰基源。由草酸盐产生的强还原性CO自由基阴离子物种在实现末端和内炔烃的整体氘代羧基化反应中发挥了重要作用,从而以高收率和氘代率获得了各种四氘代和三氘代芳基丙酸。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d717/11323338/e421c97e4ad8/d4sc03586k-f1.jpg

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