Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives

Trifluoromethylation stands as a pivotal technology in modern synthetic chemistry, playing an indispensable role in drug design, functional material development, and agrochemical innovation. With the growing emphasis on green chemistry principles, the pursuit of environmentally benign trifluoromethy...

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Main Authors: Fang-Fang Tan, Zhan-Chao Li
Format: Article
Language:English
Published: Frontiers Media S.A. 2025-05-01
Series:Frontiers in Chemistry
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Online Access:https://www.frontiersin.org/articles/10.3389/fchem.2025.1602003/full
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author Fang-Fang Tan
Fang-Fang Tan
Zhan-Chao Li
Zhan-Chao Li
author_facet Fang-Fang Tan
Fang-Fang Tan
Zhan-Chao Li
Zhan-Chao Li
author_sort Fang-Fang Tan
collection DOAJ
description Trifluoromethylation stands as a pivotal technology in modern synthetic chemistry, playing an indispensable role in drug design, functional material development, and agrochemical innovation. With the growing emphasis on green chemistry principles, the pursuit of environmentally benign trifluoromethylation strategies has emerged as a critical research frontier. Trifluoroacetic acid (TFA), characterized by its cost-effectiveness, stability, and low toxicity, has become a promising alternative to conventional trifluoromethylation reagents. This review systematically summarizes advancements in photocatalytic decarboxylative trifluoromethylation using TFA and its derivatives over the past decade, focusing on three key activation mechanisms: single-electron transfer (SET), electron donor-acceptor (EDA) complex-mediated pathways, and ligand-to-metal charge transfer (LMCT). This paradigm shift is driven by the intrinsic limitations of conventional thermal decarboxylation, particularly its reliance on harsh conditions and significant environmental burdens. In contrast, photocatalytic strategies enable efficient C–CF3 bond construction under mild conditions, offering a modular platform for synthesizing fluorinated functional molecules. Strategic research priorities should focus on overcoming fundamental challenges, including but not limited to optimizing photosensitizer catalytic efficiency, establishing regioselective manipulation strategies, and engineering multicomponent tandem reaction systems to achieve trifluoromethylation methodologies under mild conditions. Furthermore, the integration of mechanistic investigations with artificial intelligence-driven reaction prediction will accelerate the advancement of precision trifluoromethylation technologies. This progress is anticipated to provide sustainable synthetic solutions for next-generation fluorinated pharmaceuticals and advanced functional materials, effectively bridging the innovation gap between academic research and industrial implementation.
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spelling doaj-art-2ed43830b6504d21987853b167e9b0d02025-08-20T03:49:42ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462025-05-011310.3389/fchem.2025.16020031602003Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivativesFang-Fang Tan0Fang-Fang Tan1Zhan-Chao Li2Zhan-Chao Li3School of Chemistry and Materials, Weinan Normal University, Weinan, ChinaSustainable Materials and Chemistry, Department of Wood Technology and Wood-based Composites, University of Göttingen, Göttingen, GermanySchool of Chemistry and Environmental Engineering, Sichuan University of Science and Technology, Zigong, ChinaKey Laboratories of Fine Chemicals and Surfactants in Sichuan Provincial Universities, Zigong, ChinaTrifluoromethylation stands as a pivotal technology in modern synthetic chemistry, playing an indispensable role in drug design, functional material development, and agrochemical innovation. With the growing emphasis on green chemistry principles, the pursuit of environmentally benign trifluoromethylation strategies has emerged as a critical research frontier. Trifluoroacetic acid (TFA), characterized by its cost-effectiveness, stability, and low toxicity, has become a promising alternative to conventional trifluoromethylation reagents. This review systematically summarizes advancements in photocatalytic decarboxylative trifluoromethylation using TFA and its derivatives over the past decade, focusing on three key activation mechanisms: single-electron transfer (SET), electron donor-acceptor (EDA) complex-mediated pathways, and ligand-to-metal charge transfer (LMCT). This paradigm shift is driven by the intrinsic limitations of conventional thermal decarboxylation, particularly its reliance on harsh conditions and significant environmental burdens. In contrast, photocatalytic strategies enable efficient C–CF3 bond construction under mild conditions, offering a modular platform for synthesizing fluorinated functional molecules. Strategic research priorities should focus on overcoming fundamental challenges, including but not limited to optimizing photosensitizer catalytic efficiency, establishing regioselective manipulation strategies, and engineering multicomponent tandem reaction systems to achieve trifluoromethylation methodologies under mild conditions. Furthermore, the integration of mechanistic investigations with artificial intelligence-driven reaction prediction will accelerate the advancement of precision trifluoromethylation technologies. This progress is anticipated to provide sustainable synthetic solutions for next-generation fluorinated pharmaceuticals and advanced functional materials, effectively bridging the innovation gap between academic research and industrial implementation.https://www.frontiersin.org/articles/10.3389/fchem.2025.1602003/fullphotocatalysistrifluoromethylationtrifluoroacetic acid (TFA)decarboxylationradical
spellingShingle Fang-Fang Tan
Fang-Fang Tan
Zhan-Chao Li
Zhan-Chao Li
Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives
Frontiers in Chemistry
photocatalysis
trifluoromethylation
trifluoroacetic acid (TFA)
decarboxylation
radical
title Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives
title_full Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives
title_fullStr Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives
title_full_unstemmed Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives
title_short Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives
title_sort advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives
topic photocatalysis
trifluoromethylation
trifluoroacetic acid (TFA)
decarboxylation
radical
url https://www.frontiersin.org/articles/10.3389/fchem.2025.1602003/full
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