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A visible-light-induced radical cascade regioselective acylation/cyclization of 1,7-dienes with acyl oxime esters for the preparation of acylation polycyclic compounds via NCR-mediated C-C σ-bond cleavage is established. The transformation involves the cleavage of the C-C σ-bond in acyl oxime esters and selective addition of the electron neutral C═C bonds in 1,7-dienes for the synthesis of acyl polycyclic quinolinone derivatives, not the traditional seven-membered ring products. The strategy offers several advantages, including broad substrate tolerance, no need for bases, hyperstoichiometric radical initiators, and other auxiliaries.
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http://dx.doi.org/10.1021/acs.joc.4c00904 | DOI Listing |
J Org Chem
September 2025
Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation, College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming, Yunnan Province 650500, P. R. China.
Photoinduced trifluoroethyl and acyl radical procedures for the efficient and simple preparation of iodotrifluoroethylated and acylated pyrrolidine-2-ones from -tethered 1,6-enynes with 1,1,1-trifluoro-2-iodoethane and acyl oxime esters are reported. The photoinduced iodotrifluoroethylation is performed via the energy transfer (EnT) process of the fluorescein sodium-mediated atom-transfer radical addition (ATRA) strategy under visible-light irradiation. The acylation is carried out with 4CzIPN as an organophotocatalyst at room temperature under metal- and oxidant-free conditions.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong 999077, China.
Despite notable advancements in noble metal photocatalysis, improving catalyst efficiency and recyclability remains a key challenge that needs to be addressed to facilitate large-scale synthetic applications. Herein, we have successfully synthesized bisphosphine-protected gold nanoclusters with a distinctive Johnson solid kernel, which serve as efficient and recyclable heterogeneous photocatalysts for visible-light-driven three-component radical couplings in Fukuyama indole synthesis. In contrast to conventional gold complexes, the newly developed cluster-based catalysts can be easily photoexcited to their triplet states by visible light, enabling single-electron transfer with -acyl oximes, a hitherto unexplored class of electrophiles in gold photocatalysis.
View Article and Find Full Text PDFOrg Lett
June 2025
School of Petrochemical Engineering, Changzhou University, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou, Jiangsu 213164, P. R. China.
An iron-catalyzed double annulation of -acyl oximes with fumaronitrile has been developed for the concise synthesis of polysubstituted 4-cyano7-azaindoles. This method enables the construction of two fused heterocycles in a one-step reaction using readily available starting materials under redox-neutral conditions.
View Article and Find Full Text PDFOrg Lett
June 2025
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Changzhou University; Changzhou, Jiangsu 213164, P. R. China.
An iron-catalyzed [3 + 2] annulation of -acyl oximes with 2-hydroxy-1-naphthoates has been developed. This strategy features the simultaneous activation of both substrates to form two radical intermediates. Subsequent selective C-N radical coupling followed by sequential condensation and 1,3-ester migration affords 1- or 3-benzo[g]indoles.
View Article and Find Full Text PDFAnal Chem
May 2025
College of Life Sciences, Northwest University, Xi'an 710069, China.
The sensitivity, selectivity, and accuracy of immobilized protein-based methods are critically dependent on the strategies employed for protein immobilization. Compared with random immobilization approaches, site-specific covalent methods have emerged as promising alternatives, offering enhanced analytical performance. However, these methods typically require genetic modification of the target protein to incorporate a specific tag or prior purification of the protein, posing significant challenges for immobilizing endogenous proteins.
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