The favoured protonation sites leading to isomeric toluenium ions have been assayed, envisaging the mildest possible route for proton transfer to naked toluene.
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Stereoselective benzylic C(sp)-H alkenylation enabled by metallaphotoredox catalysis.
Chem Sci
August 2024
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University Nanjing 210023 China.
Article Synopsis
- The study focuses on selective activation of benzylic C(sp)-H bonds for creating complex organic compounds, highlighting the challenges associated with selecting among similar C-H bonds.
- A site- and stereoselective method is introduced using metallaphotoredox catalysis, allowing for the production of various tri- and tetrasubstituted olefins from complex substrates with multiple benzylic sites.
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Remote proton elimination: C-H activation enabled by distal acidification.
Science
May 2024
Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria.
Generally, the acidity of carbon-hydrogen bonds is most sensitive to functionality just one or two bonds away. Here, we present an approach to the formation of carbon-carbon σ bonds by remote proton elimination, a distinct mode of carbon-hydrogen activation enabled by distal acidification through five carbon-carbon bonds. Application of remote proton elimination to cyclodecyl cations unveiled an appealing method for the synthesis of decalins.
View Article and Find Full Text PDFCopper-catalysed radical-relay reactions that employ -fluorobenzenesulfonimide (NFSI) as the oxidant have emerged as highly effective methods for C(sp)-H functionalization. Herein, computational studies are paired with experimental data to investigate a series of key mechanistic features of these reactions, with a focus on issues related to site-selectivity, enantioselectivity, and C-H substrate scope. (1) The full reaction energetics of enantioselective benzylic C-H cyanation are probed, and an adduct between Cu and the -sulfonimidyl radical (˙NSI) is implicated as the species that promotes hydrogen-atom transfer (HAT) from the C-H substrate.
View Article and Find Full Text PDFContinuous Flow Electrochemistry Enables Practical and Site-Selective C-H Oxidation.
Angew Chem Int Ed Engl
October 2023
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
The selective oxygenation of ubiquitous C(sp )-H bonds remains a highly sought-after method in both academia and the chemical industry for constructing functionalized organic molecules. However, it is extremely challenging to selectively oxidize a certain C(sp )-H bond to afford alcohols due to the presence of multiple C(sp )-H bonds with similar strength and steric environment in organic molecules, and the alcohol products being prone to further oxidation. Herein, we present a practical and cost-efficient electrochemical method for the highly selective monooxygenation of benzylic C(sp )-H bonds using continuous flow reactors.
View Article and Find Full Text PDFTheoretical Investigations of Palladium-Catalyzed [3+2] Annulation via Benzylic and meta C-H Bond Activation.
Chem Asian J
September 2023
Institute of Quantum Beam Science, Graduate School of Science and Engineering, Ibaraki University, 2-1-1 Bunkyo, Mito, Ibaraki, 310-8512, Japan.
Article Synopsis
- The palladium-catalyzed reaction of aromatic amides with maleimides leads to the formation of a product through double C-H bond activation at benzylic and meta positions.
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