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A synthetic strategy for the formation of C(sp)-N bonds, particularly through a copper-catalyzed oxidative cross-coupling, is rare. Herein, we report a novel synthetic approach for the preparation of tertiary sulfonamides via copper-catalyzed intra- and intermolecular oxidative C(sp)-N cross-coupling reactions. This method allows the utilization of the readily available C(sp)-based pinacol boronate as a substrate and the tolerance of a wide range of functional groups under mild reaction conditions. The success of this strategy relies on the unprecedented additive effects of silanol and NaIO.
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http://dx.doi.org/10.1021/acs.joc.1c01759 | DOI Listing |
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.
View Article and Find Full Text PDFOrg Lett
September 2025
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China.
We demonstrate a copper-catalyzed regioselective cascade oxidative desaturation and imidation of saturated heterocycles using -fluorobenzenesulfonimide (NFSI) as both an oxidant and an imidating reagent. A broad range of substituted piperidones, lactams, and cyclic ketones with high functional group tolerance could be successfully utilized in this transformation. TEMPO-trap experiments, control experiments, and DFT calculations provided supporting evidence for the possible desaturation process.
View Article and Find Full Text PDFJ Org Chem
September 2025
Key Laboratory of Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan 750021, China.
The reaction mechanism of the excited-state copper-catalyzed cascade synthesis of α,β-unsaturated-γ-lactams from aroyl chlorides, acrylamides, and -hexanol has been systematically investigated using density functional theory (DFT) calculations. The reaction consists of four elementary steps: initiation of aroyl radical formation from aroyl chlorides by the excited-state Cu-Complex; subsequent radical relay between the aroyl radical and acrylamides leading to C-C bond formation; coupling of the C-N bond through the activation of N-H bond/coordination site migration facilitated by a Cu-Complex resulting in the formation of a five-membered ring scaffold; and then the functionalization of the γ-C of lactam to introduce alkoxy or hydride groups is achieved through electrophilic substitution. The single-carbon atom insertion is realized by the radical relay and copper-catalyzed radical polar cross-coupling strategy.
View Article and Find Full Text PDFJACS Au
August 2025
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
The generation of metal carbenes from readily available allenes represents a remarkable advance in metal carbene chemistry. However, most of these transformations are mainly restricted to the noble-metal catalysts (Au and Pt). Here, a copper-catalyzed desymmetric cyclization reaction of divinylallenes is described, enabling the practical and atom-economical synthesis of a diverse array of valuable triazolo-fused pyridazines and tetracyclic N-heterocycles by a presumable copper carbene intermediate and a highly selective 1,2-N shift process.
View Article and Find Full Text PDFScience
August 2025
Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA.
Copper-catalyzed radical C(sp)‒N coupling has become a major focus in synthetic catalysis over the past decade. However, achieving this reaction manifold by using enzymes has remained elusive. In this study, we introduce a photobiocatalytic approach for radical benzylic C(sp)‒N coupling using a copper-substituted nonheme enzyme.
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