The use of a new ZnO-supported palladium(0) nanoparticle catalyst for the cyanation of aryl halides using a relatively benign cyanide source, K4[Fe(CN)6], is described. This catalyst has been applied for the efficient cyanation of a variety of functionalized aryl bromides and activated aryl chlorides. This process circumvents the need for an additive and a ligand for the reaction and offers the advantages of high product yields, low catalyst loading (0.2 mol % Pd), and recyclability of the catalyst.
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http://dx.doi.org/10.1021/jo500820q | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides and alkylzinc reagents. The reaction is enabled by amine coordination and can use all primary, secondary, and tertiary amines. The reaction constructs two new C(sp)-C(sp) and C(sp)-C(sp) bonds and produces δ- and ε-arylamines with C(sp)-branching at the γ- and δ-positions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
The University of Arizona, Chemistry and BioChemistry, 1306 E University Blvd, CSML 638, 85719, Tucson, UNITED STATES OF AMERICA.
Diffusion-limited kinetics is a key mechanistic debate when consecutive photoelectron transfer (conPET) is discussed in photoredox catalysis. In-situ generated organic photoactive radicals can access catalytic systems as reducing as alkaline metals that can activate remarkably stable bonds. However, in many cases, the extremely short-lived transient nature of these doublet state open-shell species has led to debatable mechanistic studies, hindering adoption and development.
View Article and Find Full Text PDFLangmuir
January 2025
Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran.
Angew Chem Int Ed Engl
January 2025
Technische Universitat Dresden, Inorganic Chemistry I, GERMANY.
The catalytic potential of flexible metal-organic frameworks (MOFs) remains underexplored, particularly in solution-phase reactions. This study employs MIL-53(Cr), a prototypical "breathing" MOF capable of structural adaptation via pore size modulation, as a photocatalyst for the dehalogenation of aryl halides. Powder X-ray diffraction and pair distribution function analyses reveal that organic solvents influence pore opening, while substrates and products dynamically adjust the framework configuration during catalysis.
View Article and Find Full Text PDFNat Commun
December 2024
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China.
Owning to the versatile nature in participation of Diels-Alder (D-A) reactions, the development of efficient approaches to generate active ortho-quinodimethanes (o-QDMs) has gained much attention. However, a catalytic method involving coupling of two readily accessible components to construct o-QDMs is lacking. Herein, we describe a palladium carbene migratory insertion enabled dearomative C(sp)-H activation to form active o-QDM species through the cross-coupling of N-tosylhydrazones with aryl halides.
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