Methods for direct functionalization of C-H bonds mediated by -oxyl radicals constitute a powerful tool in modern organic synthesis. While several -oxyl radicals have been developed to date, the lack of structural diversity for these species has hampered further progress in this field. Here we designed a novel class of -oxyl radicals based on -hydroxybenzimidazole, and applied them to the direct C-H functionalization reactions. The flexibly modifiable features of these structures enabled facile tuning of their catalytic performance. Moreover, with these organoradicals, we have developed a metal-free approach for the synthesis of acyl fluorides direct C-H fluorination of aldehydes under mild conditions.
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http://dx.doi.org/10.1039/d0sc02134b | DOI Listing |
Natl Sci Rev
January 2025
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China.
Constructing 3D functional covalent organic frameworks (COFs) with both robust linkage and planar macrocycle building blocks still remains a challenge due to the difficulty in adjusting both the crystallinity and the dominant 2D structures. In addition, it is also challenging to selectively convert inert C(sp)-H bonds into value-added chemicals. Herein, robust 3D COFs, USTB-28-M (M=Co, Ni, Cu), have been polymerized from the nucleophilic aromatic substitution reaction of -symmetric 2,3,6,7,14,15-hexahydroxyltriptycene with -symmetric hexadecafluorophthalocyanine (MPcF) under solvothermal conditions.
View Article and Find Full Text PDFACS Omega
January 2025
Department of Chemistry, Federal University of Sergipe, 49400-000 São Cristóvão, SE, Brazil.
Cellulose-based materials are promising adsorbents for pollutants and other classes of compounds. Here, we report the preparation of hydrogels via chemical cross-linking of microcrystalline cellulose oxidized by the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO). The cross-linking process was carried out in the presence of modifiers such as β-cyclodextrin in order to insert hydrophobic cavities or κ-carrageenan due to the presence of negative charges along the molecular chains.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Indian Institute of Science Education and Research, Pune, Dr. Homi Bhabha Road, Pashan, Pune 411008, Maharashtra, India.
The work establishes the salt of a tetra-cationic distibane, [LSb][CFSO] = [][OTf] (CFSO = OTf), stabilized by a bis(α-iminopyridine) ligand , defying the Coulombic repulsion. The synthetic approach involved a dehydrocoupling reaction when a mixture of and Sb(OTf) in a 1:1 ratio was treated with EtSiH/LiBEtH as the hydride source. Compound [][OTf] was also achieved from [LSbCl][OTf] as a precursor and using EtSiH.
View Article and Find Full Text PDFJ Nat Prod
January 2025
Pharmacognosy Institute and Department of Pharmaceutical Sciences, College of Pharmacy, University of Illinois Chicago, Chicago, Illinois 60612, United States.
To date, quantitative analysis of proanthocyanidin (PAC) containing materials including plant extracts and fractions depends on colorimetric assays or phloroglucinolysis/thiolysis combined with UV-HPLC analysis. Such assays are of limited accuracy, particularly lack specificity, require extensive sample preparation and degradation, and need appropriate physical reference standards. To address this analytical challenge and toward our broader goal of developing new plant-sourced biomaterials that chemically and mechanically modulate the properties of dental tissue for clinical interventions, we have characterized 12 different PAC DESIGNER (Depletion and Enrichment of Select Ingredients Generating Normalized Extract Resources) materials.
View Article and Find Full Text PDFNat Commun
January 2025
Institute of Industrial Catalysis, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310032, P.R. China.
Electrochemical alcohol oxidation (EAO) represents an effective method for the production of high-value carbonyl products. However, its industrial viability is hindered by suboptimal efficiency stemming from low reaction rates. Here, we present a synergistic electrocatalysis approach that integrates an active electrode and aminoxyl radical to enhance the performance of EAO.
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