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Three-dimensionally propagated imidazolium-containing mesoporous coordination polymer and organic polymer-based platforms were successfully exploited to develop single-site heterogenized Pd-NHC catalysts for oxidative arene/heteroarene C-H functionalization reactions. The catalysts were efficient in directed arene halogenation, and nondirected arene and heteroarene arylation reactions. High catalytic activity, excellent heterogeneity and recyclability were offered by these systems making them promising candidates in the area of heterogeneous C-H functionalization, where efficient catalysts are still scarce.
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http://dx.doi.org/10.1039/d1cc04429j | DOI Listing |
Org Biomol Chem
September 2025
Department of Chemistry, Indian Institute of Technology Tirupati, Yerpedu - Venkatagiri Road, Yerpedu Post, Tirupati District, Andhra Pradesh 517619, India.
A regioselective C2-alkynylation of indoles ruthenium(II)-catalyzed C-H activation using bromoalkynes is demonstrated under both solution-phase and mechanochemical conditions. The solvent-minimized mechanochemical method delivers comparable yields with reduced reaction time and improved green metrics. Broad substrate scope, gram-scale applicability, and post-functionalization showcase the synthetic utility of this approach.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
State Key Laboratory of Antiviral Drugs, Tianjian Laboratory of Advanced Biomedical Sciences, Pingyuan Laboratory, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
The C-H functionalization represents a universal and important method for constructing new C-C bonds by carrying out reactions directly on inert C-H bonds. The major challenges are to control the site-selectivity and chemoselectivity because most complex organic compounds have many similar C-H bonds or different functional groups, such as a C═C bond or O-H bond. Here, we develop a versatile copper cluster (CuNC) with high stability and dynamic catalytic sites.
View Article and Find Full Text PDFACS Electrochem
September 2025
Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, White City Campus, Wood Lane, London W12 0BZ, United Kingdom.
The development of copper-catalyzed C-H functionalization processes is challenging due to the inefficiency of conventional chemical oxidants in regenerating the copper catalyst. This study details the development of a mediated electrosynthetic approach involving triple catalytic cycles in transient C-H functionalization to achieve efficient copper-catalyzed C-(sp)-H sulfonylation of benzylamines with sodium sulfinate salts. The triple catalytic system consists of a copper organometallic cycle for C-H functionalization, an aldehyde transient directing group (TDG) as an organocatalyst for imine formation, and a ferrocenium salt as an electrocatalyst.
View Article and Find Full Text PDFChem Sci
August 2025
Freie Universität Berlin, Institute of Chemistry and Biochemistry, Organic Chemistry Takustr. 3 14195 Berlin Germany
We describe a photomediated protocol for the trifluoromethoxylation of benzylic, aldehydic, and non-activated C-H bonds, using bis(trifluoromethyl)peroxide (BTMP, (FCO)) as the key reagent. Under catalyst-free conditions in acetone, this reaction proceeds with selective functionalization of benzylic methylene groups. Furthermore, by using tetrabutylammonium decatungstate as a photocatalyst, the scope extends to include both non-activated methylene C(sp)-H and formyl C(sp)-H bonds.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
Organic and Medicinal Chemistry Research Laboratory, School of Advanced Sciences, Vellore Institute of Technology, Vellore-632 014, Tamil Nadu, India.
An efficient synthesis and late-stage C-H functionalization of papaverine under volatile solvent-free conditions are reported. This methodology demonstrates significant potential for applications in the active pharmaceutical ingredient (API) industry, particularly for the sustainable and solvent-free synthesis of papaverine. A plausible reaction mechanism was meticulously elucidated through comprehensive control experiments.
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