A novel copper-catalyzed cross-coupling of arylsulfonyl radicals with diazo compounds is described for the synthesis of various arylsulfones under mild conditions. In this reaction, the cheap, environmentally friendly, and readily available inorganic KSO is employed as the sulfur dioxide source for providing arylsulfonyl radicals. In addition, a radical mechanism involving the insertion of sulfur dioxide with aryl radicals followed by the coupling of arylsulfonyl radicals with copper carbenes is proposed.
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http://dx.doi.org/10.1021/acs.joc.2c01443 | DOI Listing |
Org Biomol Chem
January 2025
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, P. R. China.
Succinyldiamide derivatives are important structural motifs in various natural products, pharmaceuticals, and functional materials. Herein, a novel, mild, and environmentally friendly method was developed for synthesizing functionalized succinyldiamides each containing a quaternary carbon center. This strategy was designed to involve photocatalytic decarboxylation of readily available oxalic monoamide using a non-precious metal photocatalyst, 4CzIPN, followed by a free-radical addition/Smiles rearrangement cascade reaction of -aryl--(arylsulfonyl)acrylamides.
View Article and Find Full Text PDFJ Org Chem
December 2024
Guangzhou Municipal and Guangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, the NMPA and State Key Laboratory of Respiratory Disease, School of Pharmaceutical Sciences and the Fifth Affiliated Hospital, Guangzhou Medical University, Guangzhou 511436, China.
A Pd/Cu-cocatalyzed arylation of -difluoroalkenes with arylsulfonyl chlorides, affording various defluorinative arylation/1,2-difunctionalized products, was developed. The interception of aryl radicals generated from the reduction of arylsulfonyl chlorides delivers some hypervalent Pd species, which present high reactivities and chemoselectivities toward the defluorinative arylation product formation. Besides, the nature of the electron-deficient Pd metal center is more prone to reductive elimination under acidic conditions, providing an opportunity to explore new reactivates of fluorinated alkenes into more elaborate substructures.
View Article and Find Full Text PDFJ Org Chem
October 2024
Department of Chemistry, Shanghai University, Shanghai 200444, PR China.
An efficient Cu-promoted Truce-Smiles rearrangement for the aryl-difluoromethylenation of C═C bonds by the reaction of -alkyl--(arylsulfonyl)methacrylamide and 2-bromodifluoromethyl-1,3-benzodiazole via a reductive radical-polar crossover process under mild reaction conditions is presented. The protocol enables practical access to a variety of single regioisomer α-aryl-β-difluoromethylene amides in good to excellent yields through consecutive difluoromethylenation, radical-polar crossover, 1,4-aryl migration, SO extrusion, and N-H bond formation cascade reaction.
View Article and Find Full Text PDFOrg Lett
June 2024
School of Materials Science and Chemical Engineering, Ningbo University, Zhejiang 315211, China.
Org Biomol Chem
June 2024
Department of Chemistry, Chonnam National University, Gwangju, 61186 Republic of Korea.
An electrochemical synthetic method for the synthesis of sulfinic esters and sulfonic esters from sulfonyl hydrazides was developed. Alkyl sulfinic esters were synthesized by treating sulfonyl hydrazides with trialkyl orthoformate in a DMF solvent at a constant current of 5 mA and then optimizing the reaction conditions. Conversely, alkyl sulfonic esters were exclusively obtained when the reaction was conducted in alkyl alcohol solvents at a constant current of 15 mA.
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