康 · 学术｜Reaction of the Day No. 1289

来源：市场资讯

转自：康龙化成

Scalable DecarboxylativeTrifluoromethylation by Ion-shielding Heterogeneous Photoelectrocatalysis

Yixin Chen 1,2†,YuchenHe 1,2†, YongGao 2†, Jiakun Xue 2, WeiQu 1, Jun Xuan 2,3*,Yiming Mo 1,2*

1 Collegeof Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027Zhejiang, China.

2 EngineeringResearch Center of Functional Materials Intelligent Manufacturing of ZhejiangProvince, ZJU-Hangzhou Global Scientific and Technological InnovationCenter, Zhejiang University, Hangzhou 311215, China.

3 Departmentof Chemistry, Zhejiang University, Hangzhou, 310027 Zhejiang, China.

—Science, 2024, 384,670–676

Recommended by Murong Xu_MC3

ABSTRACT: Electrochemistryoffers a sustainable synthesis route to value-added fine chemicals but is oftenconstrained by competing electron transfer between the electrode andredox-sensitive functionalities distinct from the target site. Here, wedescribe an ion-shielding heterogeneous photoelectrocatalysis strategy to impose mass-transfer limitations that invert the thermodynamicallydetermined order of electron transfer. This strategy is showcased to enable decarboxylative trifluoromethylation ofsensitive (hetero)arenes byusing trifluoroacetate, aninexpensive yet relatively inert trifluoromethylgroup (CF3) source. An ion-shielding layer, formedby trifluoroacetateanions electrostatically adsorbed on a positive molybdenum-doped tungstentrioxide (WO3) photoanode, prevents undesired electron transferbetween substrates and photogeneratedholes. The practicality of the developed method was demonstrated with robust photoanodestability (approximately 380 hours), a good substrate scope, and scalingcapability to achieve 100-gram synthesis by using photoelectrochemical flowcells.

LSVsshowing the oxidation potential of 1, 2, and CF3COO–

Comparative study of decarboxylativetrifluoromethylation under chemical, electrochemical, and photoelectrochemicalconditions. N.D., not detected

Substrate scope of Ion Shield-hPEC trifluoromethylation

Scale-upof heterogeneous photoelectrochemical trifluoromethylation