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A novel dual photoredox/copper-catalyzed three-component alkylcyanation of alkenes and 1,4-alkylcyanation of 1,3-enynes have been developed. In this radical cyanoalkylation reaction, the photoredox induced alkyl radical from sulfoxonium ylides adds to the carbon-carbon double bonds of styrenes or 1,3-enynes, and the generated benzylic or allenyl radicals couple with a Cu(II) cyanide complex to achieve selective cyanation. The reaction exhibits high chemo- and regioselectivity and a wide substrate scope, providing an efficient method for the synthesis of alkyl nitriles and allenyl nitriles in a single step.
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http://dx.doi.org/10.1021/acs.orglett.4c03998 | DOI Listing |
Org Biomol Chem
June 2025
School of Chemistry and Chemical Engineering, University of Jinan, 250022, China.
A photocatalysis/copper dual-catalyzed difluoromethylthiolation of remote unactivated C(sp)-H bonds using -fluorosulfonamides was reported. The combination of photoredox and copper catalysis led to mild reaction conditions with a broad substrate scope. Luminescence quenching experiments revealed that both -fluorosulfonamides and the copper catalyst could quench the excited state of the Ru complex.
View Article and Find Full Text PDFJ Org Chem
May 2025
School of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225009, China.
We herein report a dual visible-light photoredox- and copper-catalyzed -selective allyl trifluoromethylation reaction of allylamine by using trifluoromethylpyridinium salt (TFSP) as the trifluoromethyl radical precursor. Various thermodynamically disfavorable allyl trifluoromethylated -enamides were accessible with moderate to good isolated yields. Cuprous oxide or copper nanoclusters were crucial as the co-catalyst for this transformation.
View Article and Find Full Text PDFOrg Lett
December 2024
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China.
A novel dual photoredox/copper-catalyzed three-component alkylcyanation of alkenes and 1,4-alkylcyanation of 1,3-enynes have been developed. In this radical cyanoalkylation reaction, the photoredox induced alkyl radical from sulfoxonium ylides adds to the carbon-carbon double bonds of styrenes or 1,3-enynes, and the generated benzylic or allenyl radicals couple with a Cu(II) cyanide complex to achieve selective cyanation. The reaction exhibits high chemo- and regioselectivity and a wide substrate scope, providing an efficient method for the synthesis of alkyl nitriles and allenyl nitriles in a single step.
View Article and Find Full Text PDFNat Commun
June 2024
Department of Materials Science and Engineering and Research Institute of Advanced Materials, Seoul National University, Seoul, Republic of Korea.
Atom transfer radical polymerization (ATRP) with dual photoredox/copper catalysis combines the advantages of photo-ATRP and photoredox-mediated ATRP, utilizing visible light and ensuring broad monomer scope and solvent compatibility while minimizing side reactions. Despite its popularity, challenges include high photocatalyst (PC) loadings (10 to 1000 ppm), requiring additional purification and increasing costs. In this study, we discover a PC that functions at the sub-ppm level for ATRP through mechanism-driven PC design.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2023
School of Chemistry, University of Bristol, Cantock's Close, BS8 1TS, Bristol, UK.
Decarboxylative halogenation reactions of alkyl carboxylic acids are highly valuable reactions for the synthesis of structurally diverse alkyl halides. However, many reported protocols rely on stoichiometric strong oxidants or highly electrophilic halogenating agents. Herein, we describe visible-light photoredox-catalyzed decarboxylative halogenation reactions of N-hydroxyphthalimide-activated carboxylic acids that avoid stoichiometric oxidants and use inexpensive inorganic halide salts as the halogenating agents.
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