Herein, we describe a visible light-promoted intramolecular difluoramidation reaction of olefins. By precisely adjusting the reaction conditions, the difficult-to-control olefin radical addition process was effectively controlled. Heck-type coupling of olefins and hydrofluoroamidation of olefins, as well as difunctionalization of olefins, were successfully achieved with good selectivity.
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http://dx.doi.org/10.1039/d5cc00661a | DOI Listing |
Org Biomol Chem
March 2025
Univ Rouen Normandie, INSA Rouen Normandie, Univ Caen Normandie, ENSICAEN, CNRS, Institut CARMeN UMR 6064, F-76000 Rouen, France.
A visible-light-mediated chlorotrifluoromethylation catalyzed by a copper-based photo-redox catalyst of internal alkenes is reported. The reaction proceeds with complete regioselectivity under mild reaction conditions using commercially available FCSOCl as both the trifluoromethyl and chlorine source, leading to the synthesis of added-value chemicals with atom-economy. A vast array of internal alkenes were functionalized in decent to good yields, highlighting a great tolerance to various functional groups.
View Article and Find Full Text PDFChem Sci
March 2025
Department of Chemistry, Indian Institute of Technology Kanpur Kanpur - 208016 India
Kadcotriones and kadcoccitanes, renowned for their intricate 6/6/5-tricyclic and 6/6/5/6-tetracyclic ring systems, respectively, exhibit promising biological activities. This work proposes a biosynthetic pathway that elucidates how nature synthesizes these triterpenoids from lanosterol. Inspired by this pathway, we present the first biomimetic syntheses of kadcoccitane H and kadcotrione C methyl ester.
View Article and Find Full Text PDFOrg Lett
March 2025
Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN/MOST), Université Catholique de Louvain, Place Louis Pasteur 1 bte L4.01.02, 1348 Louvain-la-Neuve, Belgium.
A methodology for radical cross-coupling with vinylsiloxanes and pyridinium salts under nickel catalysis is described. Easily implemented from inexpensive and abundant primary amines and terminal alkynes, this Hiyama coupling provides efficient access to (), (), and ()-alkenes with selectivity control. Operating under mild conditions, this robust strategy applies to a broad range of functional groups with diverse double bond stereochemistries.
View Article and Find Full Text PDFChempluschem
March 2025
Malaviya National Institute of Technology Jaipur, Chemistry, INDIA.
The present work investigates the impact of the external electric field (EEF) on the oxidizing power of N 2 O, by employing kinetics and quantum chemical calculations. We have taken the oxidation of olefin (Ethene and cyclohexene) by N 2 O as a prototype to demonstrate the effectiveness of EEF. The investigation suggests that the reaction barrier is significantly reduced by choosing an electric field in an appropriate direction.
View Article and Find Full Text PDFJ Am Chem Soc
March 2025
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States.
We report that the cationic iridium complex (PCP)IrH catalyzes the transfer-dehydrogenation of alkanes to give alkenes and hydrogen isotope exchange (HIE) of alkanes and arenes. Contrary to established selectivity trends found for C-H activation by transition metal complexes, strained cycloalkanes, including cyclopentane, cycloheptane, and cyclooctane, undergo C-H addition much more readily than -alkanes, which in turn are much more reactive than cyclohexane. Aromatic C-H bonds also undergo H/D exchange much less rapidly than those of the strained cycloalkanes, but much more favorably than cyclohexane.
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