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Nitrogen-containing heteroaromatic cores are ubiquitous building blocks in organic chemistry. Herein, we present a family of metal-free intermolecular formal cycloaddition reactions that enable highly selective and orthogonal access to isoquinolines and pyrimidines at will. Applications of the products are complemented by a density functional theory mechanistic analysis that pinpoints the crucial factors responsible for the selectivity observed, including stoichiometry and the nature of the heteroalkyne.
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http://dx.doi.org/10.1038/ncomms10914 | DOI Listing |
Angew Chem Int Ed Engl
September 2025
State Key Laboratory of Green Pesticide, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei, 430079, P.R. China.
Radical-mediated hydroalkylation of alkenes offers a more direct and atom-economical route to α-alkylated carbonyl compounds, enabling the construction of various drug scaffolds, natural products, and functional molecules. However, traditional protocols are generally restricted to active 1,3-dicarbonyl compounds and often require oxidants, large excesses of substrates, and harsh reaction conditions. Herein, we present a photoinduced, general, and practical hydroalkylation of unactivated alkenes with amides.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2025
Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, H3A 0B8, Canada.
Organic materials with room temperature phosphorescence (RTP) are a growing research topic, with recent investigations revealing a strong effect of the crystal packing on the RTP properties. However, these relationships are difficult to decipher, as the crystal packing affects both the intermolecular interactions and the molecular conformation. Here, we report a divergent synthetic strategy to generate a family of rigid carbonyl-bridged triphenylamine (TPA)-based chromophores via metal-free transformations of the same starting material, and exploit this family to investigate the effects of crystal packing on the solid state RTP properties.
View Article and Find Full Text PDFOrg Biomol Chem
August 2025
College of Pharmacy, Qiqihar Medical University, Qiqihar, Heilongjiang, 161006, P. R. China.
This article describes an eco-friendly and atom-economical electrochemical protocol for the intermolecular [3 + 2] cycloaddition to synthesize 3-benzoylindole derivatives in synthetically viable yields. The oxidative cycloaddition proceeds under transition-metal-free and strong-oxidant-free conditions, generating H and (Me)NH as the byproducts, thereby aligning with green chemistry principles. Furthermore, the methodology exhibits exceptional synthetic versatility through successful late-stage diversification and compatibility with structurally diverse substrates.
View Article and Find Full Text PDFOrg Biomol Chem
August 2025
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou, 311121, P. R. China.
1,3-Diaryl-1-pyrazoles, serving as privileged heterocyclic scaffolds, demonstrate significant application potential in pharmaceutical development, functional materials, and agrochemical industries. This study presents a synthetic strategy based on [3 + 2] cycloaddition, achieving efficient construction of 1,3-diaryl-1-pyrazoles. A novel transition metal-free protocol was established through base-catalyzed intermolecular annulation of hydrazones with vinyl sulfoxides, followed by oxidation.
View Article and Find Full Text PDFOrg Lett
July 2025
Key Laboratory of Chemistry and Engineering of Forest Products, State Ethnic Affairs Commission, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Engineering Research Center of Low-carbon and High-quality Utilization of Forest Biomass, University of Guangxi Laboratory of Optic
By leveraging synergistic photochemical and phosphate ester catalysis, we developed a photoinduced formal ene-yne metathesis protocol enabling regioselective chromene construction via concurrent alkene C═C and imine C═N bond reorganization. A series of unexplored chromenes were synthesized in the -configuration via simultaneous formation of four new bonds. Gram-scale synthesis and mechanistic studies were conducted.
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