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Realizing the directional migration of photogenerated carriers plays an important role in improving the photocatalytic performance. Meanwhile, light-driven oxidative coupling of benzylamine under ambient conditions with an inexpensive catalyst is highly desirable for the industrial field. Herein, via in situ synthesis, defect engineering, and photodeposition, a yolk-shell nanostructured photocatalyst, NiP@OH-NH-UiO-66@CuO, featuring nickel phosphide (NiP) nanoparticles (NPs) trapped inside a defect engineered metal-organic framework (MOF, namely OH-NH-UiO-66) and CuO NPs adhering on the surface of MOFs, has been rationally fabricated for the achievement of spatial separation of oxidation/reduction cocatalyst in photocatalytic reaction systems. The yolk-shell structure can effectively avoid the aggregation of the NiP and CuO NPs. Remarkably, the separation of electron collector NiP and hole collector CuO regulates the directional movement of the photogenerated carriers and effectively improves the electron-hole separation efficiency to generate abundant reactive superoxide radicals (O) and hydroxyl radicals (OH). NiP@OH-NH-UiO-66@CuO achieves a conversion of 99% for the oxidative coupling of benzylamine into imine within 1 h at ambient temperature under visible-light irradiation. The present study provides an economical method to construct a MOF-based yolk-shell photocatalyst for the oxidative coupling of amines.
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http://dx.doi.org/10.1021/acsami.5c00582 | DOI Listing |
J Org Chem
September 2025
State Key Laboratory of Chemical Resource Engineering, Institute of Computational Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
The -di(2-pyridyl)arenes, featuring a unique structure, hold significant promise for applications in fluorescent probes, synthetic nanoparticle stabilizers, and chemical synthesis. The mechanism of Ru-catalyzed decarboxylation and heteroarylation reactions of aryl carboxylic acids to access -dipyridylarenes was elucidated using DFT calculations, which involved C-H bond activation, oxidative addition, reductive elimination, and decarboxylation processes to form -di(2-pyridyl)arenes. The rate-determining step of the reaction is the second reductive elimination step with an energy barrier of 27.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
Shenzhen Grubbs Institute, Department of Chemistry, Guangming Advanced Research Institute, and Shenzhen Key Laboratory of Cross-Coupling Reactions, Southern University of Science and Technology, Shenzhen, 518055, China.
Despite the widespread utility of transition metal-catalyzed cross-couplings in organic synthesis, the coupling of unactivated alkyl electrophiles remains challenging due to sluggish oxidative addition and competing side reactions. Here, we describe a general and practical copper-catalyzed radical deoxyalkynylation of α-unfunctionalized alcohols through a synergistic combination of Barton-McCombie deoxygenation and copper-catalyzed radical cross-coupling. Key to the success of this method lies in not only the development of rigid anionic multiple N,N,N-ligand to exert remarkable selectivity of highly reactive unactivated alkyl radicals, but also the selection of one suitable oxidant to suppress Glaser homocoupling and other side products.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19014, United States.
Phenol overoxidation has severely hindered the advancement and synthetic utility of oxidative phenol coupling for over two decades, preventing the development of general catalytic methods. Electron-deficient phenols resist selective coupling due to their high oxidation potential, while monosubstituted phenols undergo uncontrolled overoxidation, making their selective transformation highly challenging. We present a strategy that harnesses biphenol-boron complexation to suppress overoxidation, unlocking the selective catalytic oxidative coupling of both electron-deficient and monosubstituted phenols.
View Article and Find Full Text PDFJ Agric Food Chem
September 2025
Institute of Agriculture, Tokyo University of Agriculture and Technology, Tokyo 183-8509, Japan.
The -hydroxyphenyl (H) unit is an aromatic structure found in lignin, particularly abundant in compression wood and grass, and is derived from the incorporation of -coumaryl alcohol (-CMA). Although the structural and biosynthetic aspects of lignin have been extensively studied, the polymerization reactivity of H-unit during lignification remains poorly understood. In this study, horseradish peroxidase (HRP)-catalyzed homo- and co-oxidative coupling reactions (initial stage of enzymatic dehydrogenative polymerization) with -CMA and/or coniferyl alcohol (CA) were performed to investigate monolignol consumption, dilignol formation, and their potential involvement in subsequent polymerization.
View Article and Find Full Text PDFChem Rec
September 2025
Chemical Sciences and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology (CSIR-NIIST), Thiruvananthapuram, 695019, India.
The Friedländer quinoline synthesis represents a fundamental method for the construction of quinoline derivatives, a versatile class of heterocyclic compounds widely prevalent in pharmaceuticals and materials science. This synthesis traditionally involves the condensation of 2-aminoaryl ketones with carbonyl compounds, typically ketones or aldehydes, in the presence of an acid or base under reflux conditions. However, recent advancements have highlighted indirect approaches (starting from 2-aminobenzyl alcohol) to achieve the same quinoline framework, offering distinct advantages in selectivity, substrate scope, and functional group tolerance.
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