Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Июнь 16, 2023

Abstract Electrochemistry utilizes electrons as a potent, controllable, and traceless alternative to chemical oxidants or reductants, typically offers more sustainable option for achieving selective organic synthesis. Recently, the merger of electrochemistry with readily available electrophiles has been recognized viable increasingly popular methodology efficiently constructing challenging C−C C‐heteroatom bonds in manner complex molecules. In this mini‐review, we have systematically summarized most recent advances electroreductive cross‐electrophile coupling (eXEC) reactions during last decade. Our focus on electrophiles, including aryl alkyl (pseudo)halides, well small molecules such CO 2 , SO D O.

Язык: Английский

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A guide to organic electroreduction using sacrificial anodes

Chemical Society Reviews, Год журнала: 2023, Номер 52(4), С. 1168 - 1188

Опубликована: Янв. 1, 2023

This review focuses on recent advances in sacrificial anode-enabled organic electroreductions.

Язык: Английский

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Nickel/biimidazole-catalyzed electrochemical enantioselective reductive cross-coupling of aryl aziridines with aryl iodides

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Апрель 22, 2023

Here, we report an asymmetric electrochemical organonickel-catalyzed reductive cross-coupling of aryl aziridines with iodides in undivided cell, affording β-phenethylamines good to excellent enantioselectivity broad functional group tolerance. The combination cyclic voltammetry analysis the catalyst reduction potential as well electrode study provides a convenient route for reaction optimization. Overall, high efficiency this method is credited electroreduction-mediated turnover nickel instead metal reductant-mediated turnover. Mechanistic studies suggest radical pathway involved ring opening aziridines. statistical serves compare different design requirements photochemically and electrochemically mediated reactions under type mechanistic manifold.

Язык: Английский

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Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 4, 2023

Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development catalytic, easily tunable synthetic approach for stereodivergent synthesis both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report photoredox nickel dual catalytic strategy sulfonylalkenylation terminal alkynes with vinyl triflates sodium sulfinates under mild conditions. With judicious choice simple catalyst ligand, this method enables efficient divergent access to Z- E-sulfonyl-1,3-dienes same set starting materials. This features broad substrate scope, good functional compatibility, excellent chemo-, regio-, stereoselectivity. Experimental DFT mechanistic studies offer insights into observed stereoselectivity controlled by ligands.

Язык: Английский

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Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Сен. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Язык: Английский

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Room Temperature Construction of Vicinal Amino Alcohols via Electroreductive Cross-Coupling of N-Heteroarenes and Carbonyls

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 10967 - 10973

Опубликована: Апрель 19, 2023

Despite the widespread applications of α-hydroxyalkyl cyclic amines, direct and diverse access to such a class unique vicinal amino alcohols still remains, date, challenge. Here, through strategy electroreductive α-hydroxyalkylation inactive N-heteroarenes with ketones or electron-rich arylaldehydes, we describe room temperature approach for construction which features broad substrate scope, operational simplicity, high chemoselectivity, no need pressurized H2 gas transition metal catalysts. The zinc ion generated from anode oxidation plays crucial role in activation both reactants by decreasing their reduction potentials. electroreduction combination Lewis acids this work is anticipated develop more useful transformations.

Язык: Английский

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Overview of Recent Scale-Ups in Organic Electrosynthesis (2000–2023)

Organic Process Research & Development, Год журнала: 2024, Номер 28(2), С. 338 - 366

Опубликована: Янв. 18, 2024

This review summarizes examples of organic electrosynthesis from the peer-reviewed literature 2000 to 2023 that have been conducted on scales 20 g or above. A significant portion these were a ≤100 scale, while detailed reports kilogram-scale remain scarce in pharmaceutical industry. In addition chemical transformation, this also highlights type reactor used and projected productivity metric as ways compare different reports. The selected scale-ups described herein illustrate remaining challenges currently preventing routine use large-scale

Язык: Английский

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Nickel-electrocatalysed C(sp3)–C(sp3) cross-coupling of unactivated alkyl halides

Nature Catalysis, Год журнала: 2024, Номер 7(4), С. 412 - 421

Опубликована: Фев. 23, 2024

Язык: Английский

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Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Язык: Английский

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Computational Methods Enable the Prediction of Improved Catalysts for Nickel-Catalyzed Cross-Electrophile Coupling

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3043 - 3051

Опубликована: Янв. 26, 2024

Cross-electrophile coupling has emerged as an attractive and efficient method for the synthesis of C(sp2)–C(sp3) bonds. These reactions are most often catalyzed by nickel complexes nitrogenous ligands, especially 2,2′-bipyridines. Precise prediction, selection, design optimal ligands remains challenging, despite significant increases in reaction scope mechanistic understanding. Molecular parameterization statistical modeling provide a path to development improved bipyridine that will enhance selectivity existing broaden electrophiles can be coupled. Herein, we describe generation computational ligand library, correlation observed outcomes with features silico Ni-catalyzed cross-electrophile coupling. The new nitrogen-substituted display 5-fold increase product formation versus homodimerization when compared current state art. This yield was general several couplings, including challenging aryl chloride N-alkylpyridinium salt.

Язык: Английский

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