Single Electron Activation of Aryl Carboxylic Acids

Xiao-Qiang Hu,Ye-Xing Hou,Yang Gao,Zi-Kui Liu

doi:10.1016/j.isci.2020.101266

Abstract

Aryl carboxylic acids are stable and readily available in great structural diversity both from natural and well-established synthetic procedures, which make them promising starting materials in organic synthesis. The conversion of benzoic acids into high-value molecules is of great importance and have gained much interest of synthetic chemists. The recent development of single-electron (1e−) activation strategy has been esteemed as a complementary method for the transformation of benzoic acids. In this context, carboxylate groups can be selectively transferred into reactive aryl carboxylic radical, aryl radical, and acyl radical by electrocatalysis, photocatalysis, or in the presence of some SET oxidants. Based on these radical species, remarkable advancements have been achieved for the rapid formation of various chemical bonds over the past 10 years. In this review, we summarize recent advances in single electron activation of aryl carboxylic acids, with an emphasis on reaction scope, catalytic system, limitation, and underlying reaction mechanism.

Highlights

Aryl carboxylic acids have been long established as versatile building blocks for the construction of various chemical bonds (Gooben et al, 2008)
Transition metal (Ag, Cu, Pd and Rh)-catalyzed decarboxylative cross-coupling reactions provide a powerful platform for the utilization of benzoic acids, in which reactive arylÀmetal species are generated in situ with the extrusion of CO2 from the carboxylate groups (Scheme 1A) (Wei et al, 2017; Font et al, 2017; Patra and Maiti, 2017; Rodrıguez and Gooben, 2011; Weaver et al, 2011)
The development of unconventional and much milder strategies through exploration of catalytic modes is extremely important for the transformation of aryl carboxylic acids but still a challenging goal for scientists

Summary

Single Electron Activation of Aryl Carboxylic Acids

Aryl carboxylic acids are stable and readily available in great structural diversity both from natural and well-established synthetic procedures, which make them promising starting materials in organic synthesis. The recent development of single-electron (1eÀ) activation strategy has been esteemed as a complementary method for the transformation of benzoic acids. In this context, carboxylate groups can be selectively transferred into reactive aryl carboxylic radical, aryl radical, and acyl radical by electrocatalysis, photocatalysis, or in the presence of some SET oxidants. Carboxylate groups can be selectively transferred into reactive aryl carboxylic radical, aryl radical, and acyl radical by electrocatalysis, photocatalysis, or in the presence of some SET oxidants Based on these radical species, remarkable advancements have been achieved for the rapid formation of various chemical bonds over the past 10 years. We summarize recent advances in single electron activation of aryl carboxylic acids, with an emphasis on reaction scope, catalytic system, limitation, and underlying reaction mechanism

INTRODUCTION

Findings

Conclusions