C-H bond activation enables the facile synthesis of new chemicals. While C-H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C-H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C-C coupling mediated by 2D TMDCs to promote C-H activation and carbon dots synthesis. Our results shed light on 2D materials for C-H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials.
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http://dx.doi.org/10.1038/s41467-024-49783-z | DOI Listing |
Biochemistry
January 2025
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Mononuclear Fe enzymes such as heme-containing cytochrome P450 enzymes catalyze a variety of C-H activation reactions under ambient conditions, and they represent an attractive platform for engineering reactivity through changes to the native enzyme. Using density functional theory, we study both native Fe and non-native group 8 (Ru, Os) and group 9 (Ir) metal centers in an active site model of P450. We quantify how changing the metal changes spin state preferences throughout the catalytic cycle.
View Article and Find Full Text PDFNat Commun
January 2025
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, PR China.
Allylic ethers and alcohols are essential structural motifs commonly present in natural products and pharmaceuticals. Direct allylic C-H oxygenation of internal alkenes is one of the most direct methods, bypassing the necessity for an allylic leaving group that is needed in the traditional Tsuji-Trost reaction. Herein, we develop an efficient and practical method for synthesizing (E)-allyl ethers from readily available internal alkenes and alcohols or phenols via selective allylic C-H oxidation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
RIKEN: Rikagaku Kenkyujo, Center for Sustainable Resource Science, 2-1 Hirosawa, 351-0198, Wako, JAPAN.
Transition-metal-catalyzed selective and efficient activation of an inert C-H bond in an organic substrate is of importance for the development of streamlined synthetic methodologies. An attractive approach is the design of a metal catalyst capable of recognizing an organic substrate through noncovalent interactions to control reactivity and selectivity. We report here a spirobipyridine ligand that bears a hydroxy group that recognizes pyridine and quinoline substrates through hydrogen bonding, and in combination with an iridium catalyst enables site-selective C-H borylation.
View Article and Find Full Text PDFOrg Lett
January 2025
Institute of Chemistry, NAWI Graz, University of Graz, Heinrichstrasse 28, 8010 Graz, Austria.
The introduction of fluorine into organic molecules is of the utmost importance in the preparation of active pharmaceutical ingredients (APIs). While a wide range of fluorine sources for organic synthesis have been used over the past decades, the associated safety risks, cost, or environmental impact are still serious limitations. Hexafluorosilicate salts are one of the most inexpensive and readily available sources of nucleophilic fluorine, but they have so far not been used in organic synthesis.
View Article and Find Full Text PDFChem Sci
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing University Chongqing 401331 P. R. China
Reported herein is the first example of a ruthenium-catalyzed C-H activation/annulation of phenothiazine-3-carbaldehydes to construct structurally diverse pyrido[3,4-]phenothiazin-3-iums with dual-emission characteristics. Novel organic single-molecule white-light materials based on pyrido[3,4-]phenothiazin-3-iums with dual-emission and thermally activated delayed fluorescence (TADF) characteristics have been developed for the first time herein. Furthermore, the dual-emission molecule could be fabricated as water-dispersed NPs, which could be applied in two-channel emission intensity ratio imaging to observe the intercellular structure and can specifically target the cell membrane.
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