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Recyclable Cu-Catalyzed -Methylation and C5-Methylthiomethylation of Isatins with DMSO.

J Org Chem

September 2025

Guangxi Key Laboratory of Electrochemical and Magneto-Chemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, China.

An unprecedented recyclable system of copper-catalyzed C-C/N coupling of isatins and DMSO without any oxidant and acidic/basic additive has been unlocked. The -isatins occur tandem -methylation and C5-methylthiomethylation in order, while -substituted isatins proceed C5-methylthiomethylation only. DMSO serves as Me and MeSCH sources as well as the solvent.

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Aryl sulfinamides are valuable intermediates and functional motifs in organic synthesis, with broad utility in pharmaceutical and agrochemical development. However, their broader application has been limited by underdeveloped synthetic methods, often requiring conventionally prefunctionalized aryl/alkenyl halides or organometallic reagents, protected sulfinylamine reagents, and harsh reaction conditions. Herein, we report a photo/copper-catalyzed sulfinamidation of arenes and alkenes, employing aryl and alkenyl sulfonium salts as radical linchpins.

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A series of sulfonium, selenonium, and ammonium salts featuring diverse benzylidene acetal side chain substituents are designed and synthesized. In contrast to the previous work, this study emphasized stereochemical inversion at the 3'-position and bioisosteric replacements at the sulfonium cationic center. In vitro α-glucosidase inhibition assays identified 20b, 20l, and 21b as potent inhibitors.

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Recent advances in metalloporphyrin-catalyzed fluorinated carbene transfer reactions.

Chem Commun (Camb)

August 2025

State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

Over the past two decades, metalloporphyrin-catalyzed fluorinated carbene transfer reactions have achieved remarkable progress in the field of organofluorine chemistry. This review summarizes the applications of metalloporphyrins in catalyzing the transfer of fluorinated carbenes, including trifluoromethylcarbene, difluoromethylcarbene, monofluorocarbene and difluorocarbene, reported since 2006. The catalysts exhibit excellent activity, substrate adaptability, and selectivity, while the novel carbene precursors, such as sulfonium salts and sulfonylhydrazones enhance operational safety and reaction efficiency.

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Despite the significant applications of fluorinated cyclobutanes in industrial and diagnostic fields, efficient methods for synthesizing these valuable fluorinated structures remain limited. Here, we report a new difluoroalkylating reagent, 2-(difluoromethylene)cyclobutyl sulfonium salts (CB-DFASs). This reagent can be readily synthesized on a gram scale in three steps from readily available cyclobutanone enol silyl ether.

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