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Thiols and thioesters play crucial roles in pharmaceuticals, biology, and material science as essential organosulfur compounds. Leveraging readily available and cost-effective inert alkanes through direct thioetherification holds promise for yielding high-value-added products. Herein, we present a photoinduced strategy for sulfur-containing modification of inert alkanes utilizing decatungstate as hydrogen atom transfer reagent, offering a straightforward and practical approach for synthesizing thioethers and thioesters.
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http://dx.doi.org/10.1039/d4ob00394b | DOI Listing |
Top Curr Chem (Cham)
August 2025
Endocrinology and Metabolism Research Center, Endocrinology and Metabolism Clinical Sciences Institute, Tehran University of Medical Sciences, Tehran, Iran.
The direct functionalization of unactivated C(sp)-H bonds is crucial for the synthesis of organic compounds, enabling the efficient generation of C(sp)-X bonds (X = carbon, heteroatom) in natural products and pharmaceuticals. Despite the natural inertness of these bonds and the challenges associated with regioselectivity in alkanes, various approaches, primarily coordination-assisted and radical methods, have been developed to address these issues and enable effective catalytic activation. This review provides a comprehensive overview of transition-metal-catalyzed direct functionalization of nonactivated C(sp)-H bonds.
View Article and Find Full Text PDFOrg Lett
September 2025
College of Pharmacy, Nanjing University of Chinese Medicine, Nanjing 210000, People's Republic of China.
An efficient and selective copper-catalyzed secondary C(sp)-H esterification has been developed. The reaction of various alkane substrates with azidobenziodoxole derivatives, in the presence of a cuprous iodide catalyst and trifluoromethanesulfonic acid additive, afforded inert aliphatic C-H esterification products. These reactions are selective and compatible with a wide range of functional groups.
View Article and Find Full Text PDFSmall
August 2025
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116012, P. R. China.
Partial oxidation of alkanes with green O source for valuable oxygenated products is one of the most challenging tasks in chemistry due to the difficulty of the activation of both inert C(sp)─H bonds and unreactive O molecules. Taking advantage of the structural designability of covalent organic frameworks (COFs) for incorporating diverse functional groups and embedding redox-active Fe/Cu ions into a bipyridine-based COF (BPY-COF), metalated COFs (M@COFs; M = Fe, Cu) with open coordinative metal sites are obtained as heterogeneous photocatalysts for the activation and aerobic oxidation of alkanes under mild conditions. Photoinduced activation of the C(sp)-H bonds is achieved via hydrogen atom transfer (HAT) by chlorine radicals (Cl•), which are generated via ligand-to-metal charge transfer (LMCT) between the metal centers in the M@COFs and chlorine ions; and the M@COFs with good photoelectric performance can activate O via photoinduced electron transfer (PET).
View Article and Find Full Text PDFJ Chem Phys
August 2025
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China.
Light alkanes, such as methane, ethane, and propane, are pivotal feedstocks in the chemical industry. However, their activation and transformation remain challenging due to the intrinsic chemical inertness of the C(sp3)-H bonds, particularly under mild reaction conditions. Gas-phase metal clusters serve as an ideal platform for probing mechanisms of alkane activation at a molecular level.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, China.
The direct functionalization of alkanes remains a formidable challenge in synthetic chemistry. Herein, we present an integrated plasma-microdroplet approach for the efficient conversion of alkanes into imines under mild conditions. By employing plasma discharge in a nitrogen atmosphere, inert C-H bonds are selectively activated, generating abundant N-insertion intermediates.
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