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An additive-free trifluoromethylation-heteroarylation of enamides with trifluoromethyl heteroaryl sulfones via EDA photochemistry is reported. Under visible-light irradiation, diverse enamides and sulfones undergo efficient difunctionalization to afford CF-heteroaryl amides in moderate to excellent yields, without the need for photocatalysts or additives. Mechanistic studies support the formation of a photoexcited EDA complex that triggers C-S bond cleavage, generating CF and heteroaryl anions. This work provides a sustainable approach to alkene arylative difunctionalization and expands the utility of aryl sulfones in constructing CF-containing scaffolds.
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http://dx.doi.org/10.1021/acs.orglett.5c02330 | DOI Listing |
Org Lett
August 2025
National Key Laboratory for the Development and Utilization of Forest Food Resources, Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing, Jiangsu 210037, China.
An additive-free trifluoromethylation-heteroarylation of enamides with trifluoromethyl heteroaryl sulfones via EDA photochemistry is reported. Under visible-light irradiation, diverse enamides and sulfones undergo efficient difunctionalization to afford CF-heteroaryl amides in moderate to excellent yields, without the need for photocatalysts or additives. Mechanistic studies support the formation of a photoexcited EDA complex that triggers C-S bond cleavage, generating CF and heteroaryl anions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, Lausanne, CH-1015, Switzerland.
Bicyclo[1.1.1]pentanes (BCPs) are well-studied bioisosteres for para-substituted benzene rings, and numerous methods for synthesizing 1,3-difunctionalized BCPs have been developed.
View Article and Find Full Text PDFJ Org Chem
May 2025
School of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225009, China.
We herein report a dual visible-light photoredox- and copper-catalyzed -selective allyl trifluoromethylation reaction of allylamine by using trifluoromethylpyridinium salt (TFSP) as the trifluoromethyl radical precursor. Various thermodynamically disfavorable allyl trifluoromethylated -enamides were accessible with moderate to good isolated yields. Cuprous oxide or copper nanoclusters were crucial as the co-catalyst for this transformation.
View Article and Find Full Text PDFOrg Biomol Chem
February 2025
School of Petrochemical Engineering, Changzhou University, Changzhou 213164, P. R. China.
A Heck-type alkylation of enamides with -trifluoroethyl hydroxylamine reagents was developed under photocatalytic conditions. This stereoselective reaction provides amido-substituted ()-α-trifluoromethyl allylamines in yields up to 96%. In the mechanism, photoredox-induced 1,2-H shift of the generated -trifluoroethyl radical was involved.
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