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A novel dehydrogenative coupling reaction of -fluorocarboxamides with polyfluoroarenes forming C(sp)-C(sp) bonds enabled by copper catalysis has been accomplished. -Fluorocarboxamides are postulated to undergo copper-mediated dehydrogenative cross-coupling reaction with electron-deficient polyfluoroarenes via a radical pathway. Benzylic C-H bonds and aliphatic C-H bonds in -fluorocarboxamides could proceed smoothly and demonstrated excellent regioselectivity. The detailed mechanism presented is supported by control experiments and density functional theory calculations.
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http://dx.doi.org/10.1021/acs.orglett.1c00586 | DOI Listing |
Org Lett
September 2025
Enamine Ltd., Chervonotkatska 78, 02094 Kyiv, Ukraine.
Photochemical decatungstate-catalyzed functionalization of C-H bonds with vinyl sulfonyl fluoride (CH═CHSOF) in flow leads to the rapid formation of aliphatic sulfonyl fluorides. This reaction is compatible with the simplest, inexpensive C-H substrates, such as PhCHO, DMF, CHCl, EtOH, cyclohexane, etc. The products are obtained in milligram, gram, and even multigram quantities (up to 265 g).
View Article and Find Full Text PDFJ Phys Chem A
September 2025
Department of Inorganic and Physical Chemistry, Indian Institute of Science Bangalore, Bengaluru560012, India.
The microwave spectrum of the complex formed between 1-fluoronaphthalene and HO has been recorded using a chirped pulse Fourier transform microwave spectrometer within the frequency range of 2.0 to 8.0 GHz, with neon as the carrier gas.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
State Key Laboratory of Antiviral Drugs, Tianjian Laboratory of Advanced Biomedical Sciences, Pingyuan Laboratory, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
The C-H functionalization represents a universal and important method for constructing new C-C bonds by carrying out reactions directly on inert C-H bonds. The major challenges are to control the site-selectivity and chemoselectivity because most complex organic compounds have many similar C-H bonds or different functional groups, such as a C═C bond or O-H bond. Here, we develop a versatile copper cluster (CuNC) with high stability and dynamic catalytic sites.
View Article and Find Full Text PDFChem Sci
August 2025
Freie Universität Berlin, Institute of Chemistry and Biochemistry, Organic Chemistry Takustr. 3 14195 Berlin Germany
We describe a photomediated protocol for the trifluoromethoxylation of benzylic, aldehydic, and non-activated C-H bonds, using bis(trifluoromethyl)peroxide (BTMP, (FCO)) as the key reagent. Under catalyst-free conditions in acetone, this reaction proceeds with selective functionalization of benzylic methylene groups. Furthermore, by using tetrabutylammonium decatungstate as a photocatalyst, the scope extends to include both non-activated methylene C(sp)-H and formyl C(sp)-H bonds.
View Article and Find Full Text PDFNat Chem
September 2025
Division of Medicinal and Process Chemistry, CSIR-Central Drug Research Institute, Lucknow, India.
[2,1]-Azaboranaphthalenes represent unique boron-nitrogen (BN) isosteres of naphthalenes, attracting interest for the development of molecules with enhanced therapeutic potency. The existing synthetic strategies are generally two-component reactions with harsh conditions. Here we report an organocatalysed three-component modular synthesis of ring-fused BN isosteres and BN-2,1-azaboranaphthalenes following ring expansion of unstrained cyclic ketones (n = 4-8) via Wolff-type rearrangement.
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