Organo-mediator enabled electrochemical transformations

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review highlights organo-mediators that enable electrochemical reactions via outer-sphere electron transfer (ET), offering advantages such as availability, tunability, and simplified post-processing compared to direct electrolysis.

Language: Английский

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Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

ConspectusElectrochemistry has been used as a tool to drive chemical reactions for more than two centuries. With the help of an electrode and power source, chemists are provided with system whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable oxidizing or reducing some most tenacious compounds. Indeed, electroreduction offers alternative generating highly active intermediates from electrophiles (e.g., halides, alkenes, etc.) in organic synthesis, which untouchable traditional reduction methods. Meanwhile, reductive coupling extensively utilized both industrial academic settings due their ability swiftly, accurately, effectively construct C–C C–X bonds, present innovative approaches synthesizing complex molecules. Nonetheless, its application is constrained by several inherent limitations: (a) requirement stoichiometric quantities agents, (b) scarce activation strategies inert substrates high potentials, (c) incomplete mechanistic elucidation, (d) challenges isolation intermediates. merging represents attractive approach address above limitations synthesis seen increasing use synthetic community over past few years.Since 2020, our group dedicated developing electroreductive cross-coupling using readily available small molecules, such arenes, CO2, D2O, value-added products. Electroreductive chemistry versatile powerful capacity precise selectivity control, allowed us develop three electrochemical modes lab: (1) An economically advantageous direct (EDR) strategy that emphasizes efficiency, achieves atom utilization, minimizes unnecessary atomic waste. (2) A class organo-mediated (EOMR) methods controlling reaction pathways. This allows modulation processes enhance efficiency selectivity. (3) metal-catalyzed (EMCR) method enables selective functionalization specific bonds functional groups under mild conditions, thereby occurrence side reactions. We commenced studies establishing organic-mediator-promoted carboxylation aryl alkyl halides. was then employed arylcarboxylation simple styrenes halides manner. electrolysis arenes epoxides CO2 carboxyl source achieved. Moreover, through adjustment we successfully accomplished deuteration olefins, unactivated enabling efficient formation D-labeled Finally, building on previous understanding developed series alkylation enable C(sp3)–C(sp3)

Language: Английский

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The Electrosynthesis of Highly Encumbered Biaryls from Aryl o-Iodobenzyl Ethers by a Radical to Polar Crossover Sequence.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Highly encumbered 2,2',6-tri- and 2,2',6,6'-tetra-substituted biaryls are readily prepared from aryl ortho-iodobenzyl ethers through mediated cathodic reduction under flow. The reaction proceeds via the stepwise transfer of two electrons: first to induce loss iodide a radical cyclisation, second polar fragmentation.

Language: Английский

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Electrochemical Benzylic C–H Carboxylation

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Direct benzylic C-H carboxylation stands as a high atom economy, efficient, and convenient route for the synthesis of valuable carboxylic acids, which are great significance in many pharmaceuticals bioactive molecules. However, inherent inertness both bonds carbon dioxide presents challenge further transformations. Herein, we report our efforts to overcome this obstacle via halide-promoted linear paired electrolysis generate various acids. Remarkably, process is transition-metal- base-free, making it environmentally benign cost-effective. Besides, suitable constructing wide range primary, secondary, tertiary acids under mild reaction conditions, demonstrating broad substrate scopes good functional group tolerance. Furthermore, protocol enables direct some drug molecules, including Flurbiprofen, Ibuprofen, Naproxen, facilitates late-stage modification complex compounds, showcasing practical application synthetic chemistry underscores its potential advance related compounds.

Language: Английский

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A general electrochemical CO2 fixation to aromatic carboxylic acids via the CO2·− intermediate using a non-transition metal electrode

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

Language: Английский

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Electrochemical β-selective silylcarboxylation of styrenes with CO2

Science Bulletin, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

Language: Английский

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