Electrochemical C−H deuteration of pyridine derivatives with D2O

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 7, 2024

Herein, we develop a straightforward, metal-free, and acid-/base-free electrochemical C4-selective C - H deuteration of pyridine derivatives with economic convenient D

Язык: Английский

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Electrocatalytic Alkene Hydrogenation/Deuteration

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 4, 2025

Traditional reductions of alkenes, such as using stoichiometric reductants with waste generation and catalytic hydrogenation high-pressure H2, are accompanied by environmental or safety issues. Herein, we demonstrated a universal method for the electrocatalytic deuteration alkenes modified electrodes under ambient temperature. The key M-H/M-D species alkene reduction were generated from electrolysis H2O/D2O on electrodes, which avoided usage H2 D2. Mono-, di-, tri-, tetra-substituted successfully reduced in this system H2O D2O hydrogen deuterium sources. Electron-donating/-withdrawing other easily reducible functional groups, complicated natural products drugs all reductive hydrogenated deuterated excellent yields (85 examples, up to 99%). Faraday efficiency efficient could reach 84%. Moreover, amount metal decrease less than 0.01 mol %.

Язык: Английский

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Organo-mediator enabled electrochemical transformations

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

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Electrochemical conversion of organic compounds and inorganic small molecules

Science China Chemistry, Год журнала: 2024, Номер 67(10), С. 3223 - 3246

Опубликована: Июль 9, 2024

Язык: Английский

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

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Дек. 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)

Язык: Английский

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Pd-Catalyzed Asymmetric Etherification of 2H-chromenes: Enantioselective Construction of Chiral 4-Alkoxy-4H-chromenes

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A new strategy for the construction of a chiral 4-alkoxy-4 H -chromene skeleton was reported. series -chromenes containing trifluoromethyl group were obtained in good yields and excellent enantioselectivity.

Язык: Английский

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Electrochemical cobalt-catalyzed semi-deuteration of alkynes to access deuterated Z-alkenes

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 10, 2025

Abstract Deuterium labeling has found extensive applications across various research fields, including organic synthesis, drug design, and molecular imaging. Electrocatalytic semi-hydrogenation of alkynes offers a viable route for the synthesis Z -alkenes, yet it falls short in achieving semi-deuteration these compounds. In this study, we report an electrochemical cobalt-catalyzed transfer deuteration reaction that proficiently accomplishes alkynes, yielding -configuration deuterated alkene products. This utilizes cost-effective cobalt salts as catalysts employs D 2 O AcOD (acetic acid- d ) economical efficient deuterium sources, underscoring its practicality feasibility. The demonstrates broad alkyne substrate scope, high efficiency, good functional group compatibility, excellent -selectivity, remarkable degree rate.

Язык: Английский

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Electrocatalytic Hydrogenation of Olefins

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

Abstract Electrochemical synthesis offers a powerful and sustainable alternative to conventional chemical manufacturing techniques. The direct selective electrohydrogenation of olefins has enormous potential applicability; however, this reactivity not been sufficiently demonstrated. Herein, we show that an efficient Pt‐based electrocatalyst from commercially available PtCl 2 can promote such transformations. This approach enables be electrohydrogenated (often below −3.0 V vs. Ag/AgCl) at high current density ( J Geo up 133 mA cm −2 ) using protons electrons as the hydrogen source. reaction exhibits broad functional group compatibility, requires low catalyst loading, affords diverse series valuable molecules (more than 60 examples) with chemoselectivity. In addition, highly regioselective electrocatalytic hydrogenation (r.r. > 19:1) is demonstrated 2,2′‐bipyridine.

Язык: Английский

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Proton-Modulated Nickel Hydride Electrocatalysis for the Hydrogenation of Unsaturated Bonds and Olefin Isomerization

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 21, 2025

Transition-metal hydrides stand as indispensable intermediates in both energy conversion and organic synthesis. Their electrochemical generation represents a compelling sustainable approach, enabling precise control over the reactivity expanding scope of electrocatalytic hydrogenation isomerization. However, major challenge Ni-catalyzed is competing hydrogen evolution reaction (HER), which has led to various innovative strategies aimed at circumventing Ni-H formation. Here, we pursued an alternative approach by designing bifunctional ligand with pendant amine moiety promote This design enabled selective (semi)hydrogenation diverse range substrates, including terminal internal alkynes, alkenes, aldehydes, achieving unprecedented substrate scope. Remarkably, also demonstrated tunable positional selectivity for olefin isomerization employing different types proton sources. Our method exhibits excellent functional group tolerance, streamlining access pharmaceuticals their derivatives. Computational studies revealed crucial, noninnocent role source modulating metal hydride selectivity, either through bonding, direct protonation amine, or facilitation protodemetalation.

Язык: Английский

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Electricity-driven organic hydrogenation using water as the hydrogen source

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Employing water as a hydrogen source is an attractive and sustainable option in electricity-driven organic hydrogenation, which can overcome the drawbacks associated with traditional sources like H 2 .

Язык: Английский

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