-Containing heterocycles are important scaffolds due to their ubiquitous presence in bioactive compounds. Their synthesis has been considered as an important research field. In this work we report the access to 6- and 7-membered rings a photoinduced strategy. To our knowledge, this work represents the first exemple of photo-induced 7--trig cyclization with -centered radicals.
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http://dx.doi.org/10.1039/d2cc02780a | DOI Listing |
J Am Chem Soc
January 2025
Institut für Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34-36, D-14195 Berlin, Germany.
Herein, we report the solvent-dependent reactivity of Fe(CO) toward AsF in either anhydrous HF or liquid SO. The reaction of Fe(CO) with the superacid HF/AsF leads to the protonation of the iron center and allows for the first-time structural characterization of [FeH(CO)] in the solid state, representing one of the most acidic transition metal hydride complexes to ever be isolated and structurally characterized. In the aprotic but oxidation-stable solvent SO, Fe(CO) is oxidized and dimerized to [Fe(CO)], which is isoelectronic with well-known Mn(CO).
View Article and Find Full Text PDFJ Org Chem
January 2025
Faculty of Science, Kunming University of Science and Technology, Jingming South Road 727, Chenggong District, Kunming 650500, P. R. China.
A novel silver-catalyzed cascade radical isonitrile insertion and defluorinative cyclization have been developed to synthesize CFH- and phosphinoyl-containing quinolines from -isocyanyl α-trifluoromethylstyrenes. The reaction proceeded under redox-neutral conditions and allowed the construction of a highly attractive quinoline ring system, with the simultaneous formation of the CFH group and introduction of various phosphinoyl groups in a single transformation, showing operational simplicity, a wide substrate scope, good tolerance for functional groups, and remarkable atom-/stepeconomy. Mechanistic studies indicated that the reaction is likely to involve the participation of P-centered radicals and key carbanion intermediates.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Institute of Materials Research and Engineering, Sensor and Flexible Electronics, 2 Fusionopolis Way, 138634, SINGAPORE.
Radical covalent organic frameworks (RCOFs) have demonstrated significant potential in redox catalysis and energy conversion applications. However, the synthesis of stable RCOFs with well-defined neutral carbon radical centers is challenging due to the inherent radical instability, limited synthetic methods and characterization difficulties. Building upon the understanding of stable carbon radicals and structural modulations for preparing crystalline COFs, herein we report the synthesis of a crystalline carbon-centered RCOF through a facile post-oxidation process.
View Article and Find Full Text PDFEnviron Sci Technol
January 2025
Department of Chemistry, University of Alberta, Edmonton Alberta T6G 2G2, Canada.
Trifluoroacetic acid (TFA) is a ubiquitous environmental contaminant; however, its sources are poorly constrained. One understudied source is from the photochemical reactions of aromatic compounds containing -CF moieties (aryl-CF) including many pharmaceuticals and agrochemicals. Here, we studied the aqueous photochemistry of 4-(trifluoromethyl)phenol (4-TFMP), a known transformation product of the pharmaceutical fluoxetine.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
The direct synthesis of C(sp)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there is a strong impetus to develop new methods by which to access sp-rich molecules from commercial feedstocks, such as alkenes.
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