Late-stage direct functionalization of the C-H bond is synthetically desirable. Metalloenzymes having metal-oxo active sites are well known to selectively catalyze hydroxylation and halogenation reactions with high efficiency. This review highlights the recent developments in the field of direct C-H halogenation and pseudohalogenation reactions catalyzed by the functional models of metalloenzymes.
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http://dx.doi.org/10.1039/d0dt02533j | DOI Listing |
Molecules
January 2025
Key Laboratory of Molecular Pharmacology and Drug Evaluation, Ministry of Education, School of Pharmacy, Yantai University, Yantai 264005, China.
A Cu-promoted highly chemoselective dimerization of 5-aminopyrazoles to produce pyrazole-fused pyridazines and pyrazines is reported. The protocol generates switchable products via the direct coupling of C-H/N-H, C-H/C-H and N-H/N-H bonds, with the merits of broad substrate scope and high functional group compatibility. Gram-scale experiments demonstrated the potential applications of this reaction.
View Article and Find Full Text PDFMolecules
January 2025
School of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China.
Isoindigo (IID)-based non-fullerene acceptors, known for their broad absorption spectra and high charge carrier mobilities, play a crucial role in organic photovoltaics. In this study, two A-DA'D-A type unfused ring acceptors (URAs), IDC8CP-IC and IDC6CP-IC, were designed and synthesized using cyclopentadithiophene (CPDT) and IID core units, each functionalized with different alkyl chains (2-hexyldecyl and 2-octyldodecyl), through an atom- and step-efficient direct C-H arylation (DACH) method. Both URAs, despite the absence of non-covalent conformation locking between CPDT and IID, demonstrated favorable molecular planarity, broad absorption ranges, low band gaps, and high molar absorption coefficients.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Anhui Normal University, School of Chemistry and Materials Science, 189 Jiuhua South Road, 241002, Wuhu, CHINA.
Achieving axially chiral biaryl dialdehydes through asymmetric catalysis remains significantly challenging due to the lack of efficient strategies. In this report, we developed a rhodium-catalyzed enantioselective C-H amidation through chiral transient directing group strategy. With this new approach, a series of axially chiral amido dialdehydes were achieved in up to 86% yields with 99.
View Article and Find Full Text PDFLangmuir
January 2025
Surface Science Laboratory, Graduate School of Engineering, Toyota Technological Institute, 2-12-1, Hisakata, Tempaku, Nagoya, Aichi 468-8511, Japan.
Hydrogen-substituted graphdiyne (HsGDY) is a two-dimensional material with an sp-sp carbon skeleton featuring a band gap and a porous structure that enhances ion diffusion. In previous reports, HsGDY growth was limited to metal substrates such as Cu, which then required transfer. Here, we developed a sandwich method that allows HsGDY to be grown directly on the target substrate.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-10691 Stockholm, Sweden.
Direct cross-coupling reactions between two similar unactivated partners are challenging but constitute a powerful strategy for the creation of new carbon-carbon bonds in organic synthesis. [4]Dendralenes are a class of acyclic branched conjugated oligoenes with great synthetic potential for the rapid generation of structural complexity, yet the chemistry of [4]dendralenes remains an unexplored field due to their limited accessibility. Herein, we report a highly selective palladium-catalyzed oxidative cross-coupling of two allenes with the presence of a directing olefin in one of the allenes, enabling the facile synthesis of a broad range of functionalized [4]dendralenes in a convergent modular manner.
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