（来源：康龙化成）

转自：康龙化成

Decarboxylative Cross-Acyl Coupling of Carboxylic Acids with Aldehydes Enabled by Nickel/Photoredox Catalysis

Xiao-Biao Yan,* Ying-Qi Liu, Ning Wang, Tao Zhang, Danqing Li, Zhicai Wang, YunzhiLin*a and Kui Zhang*b

a Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou 310030, China

b School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma’an shan 243032, China

—J. Am. Soc. Chem., 2025, DOI: 10.1021/jacs.5c00372

Recommended by Chaoyou Liu _ PDM

KEYWORDS:Photo chemistry, Decarboxylation, Decarboxylative cross-acyl coupling (反应类型), C(sp3)−C(sp2) (成键类型) Carboxylic Acids, aldehydes (原料), Ketones (产物)

ABSTRACT: Prof. Kui Zhang et al present a general method for accessing unsymmetrical alkyl−aryl and alkyl−alkyl ketones via nickel/photoredox catalyzed decarboxylative cross-acyl coupling reactions between carboxylic acids and aldehydes without the need for an additional preactivation procedure. Specifically, by using the peroxide as both an oxidant and hydrogen atom transfer (HAT) reagent, authors achieved the unprecedented combination of oxidative single electron transfer (SET) of carboxylates and HAT of aldehydes, in which the generated alkyl and acyl radicals were chemoselectively coupled by nickel catalysis. This method features a broad substrate scope with good functional group compatibility and offers new access to structurally diverse ketones.

Substrate Scope for Direct Decarboxylative Cross-Acyl Coupling

Mechanistic Studies and Proposed Mechanism

In conclusion, Prof.Kui Zhang et al have developed a general method for a direct decarboxylative cross-acyl coupling reaction to afford a diverse array of unsymmetrical alkyl−aryl and alkyl−alkyl ketones. This protocol enables the generation of alkyl and acyl radicals directly from simple and readily accessible carboxylic acid and aldehyde feedstock chemicals using peroxide to leverage the combination of oxidative SET of carboxylates and HAT of aldehydes. This method features a broad substrate scope and good functional group tolerance, thereby suggesting that it can be a practical alternative to established protocols. The synthetic utility of this method was demonstrated by valuable ketone intermediate synthesis for complex molecules and application to the late-stage functionalization of biologically active molecules.