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This work presents a site-selective C-H annulation strategy for dihydrobenzoisoxazole synthesis using readily accessible thianthrenium salts as aryne precursors. The process involves base-mediated generation of reactive aryne intermediates from thianthrenium salts followed by regioselective [3 + 2] cycloaddition with nitrone 1,3-dipoles, exhibiting excellent functional group tolerance and exceptional regiocontrol. The synthetic utility of this protocol is highlighted by the successful annulation of commercially available drug molecules, providing expedient access to novel scaffolds with potential bioactivity.
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http://dx.doi.org/10.1021/acs.joc.5c01106 | DOI Listing |
Org Lett
August 2025
College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China.
Unprotected β-arylethylamines and their derivatives serve as prominently featured structural units in biological molecules. However, most of the reactions reported to date focus on intramolecular and two-component reactions with certain limitations. There is an urgent need for an efficient strategy with a wider range of substrates compared to those of previous methods.
View Article and Find Full Text PDFJ Org Chem
August 2025
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, P. R. China.
A photocatalytic strategy for synthesizing 3-sulfonated vinylsilanes through photoinduced radical sulfur dioxide insertion into α-bromoallylsilane is presented. Using aryldiazonium or thianthrenium salts as aryl radical precursors, the reaction operates under mild conditions with various photocatalysts and SO sources. It exhibits a broad substrate scope, especially offering a practical approach for late-stage modification of drug molecules by providing valuable sulfone-containing vinylsilanes.
View Article and Find Full Text PDFOrg Lett
July 2025
College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, Shandong 266042, P. R. China.
The photoactivation of electron donor-acceptor complexes has been developed as a renewable, selective, and multifunctional strategy to generate free radicals. Nevertheless, efforts to employ catalytic amounts of organic amines as electron donors in visible-light-promoted reactions are still at a nascent stage. Herein, a novel triarylamine-based electron donor-acceptor complex has been proposed for the successful construction of β-cyanosulfone, enabling a three-component olefinic difunctionalization of aryl thianthrenium salts, (DABCO)·(SO), and cyanohydrins under visible light conditions through intramolecular 1,4-cyano migration.
View Article and Find Full Text PDFJ Org Chem
July 2025
Key Laboratory of General Chemistry of the National Ethnic Affairs Commission, School of Chemistry and Environment, Southwest Minzu University, Chengdu 610041, China.
An efficient synthesis of pyrroloquinolines has been developed via the aza-Michael/epoxidation cascade process in a diastereospecific manner. The domino reaction occurred properly to afford the desired tetracyclic indoles in 50->99% isolated yields. This synthetic protocol displayed especially broad substrate generality with respect to both indole-7-carbaldehydes and vinylsulfonium salts.
View Article and Find Full Text PDFOrg Lett
July 2025
State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China.
C-C bond formation catalyzed by abundant and nontoxic iron has attracted increasing attention. Although much progress has been made, iron-catalyzed reductive coupling is still limited. In this work, the reductive carboxylation of aryl thianthrenium salts with CO catalyzed by iron is developed.
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