Electrocatalysis as an enabling technology for organic synthesis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(14), P. 7941 - 8002

Published: Jan. 1, 2021

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and ion intermediates in controlled fashion under mild conditions inspired development number new electrochemical methodologies preparation valuable chemical motifs. Particularly, recent developments electrosynthesis have featured an use redox-active electrocatalysts further enhance control over selective formation downstream reactivity these intermediates. Furthermore, electrocatalytic mediators enable proceed manner that is mechanistically distinct from purely methods, allowing subversion kinetic thermodynamic obstacles encountered conventional synthesis. This review highlights key innovations within past decade area electrocatalysis, with emphasis on mechanisms catalyst design principles underpinning advancements. A host oxidative reductive are discussed grouped according classification transformation nature electrocatalyst.

Language: Английский

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Designing Sites in Heterogeneous Catalysis: Are We Reaching Selectivities Competitive With Those of Homogeneous Catalysts?

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(9), P. 8594 - 8757

Published: March 3, 2022

A critical review of different prominent nanotechnologies adapted to catalysis is provided, with focus on how they contribute the improvement selectivity in heterogeneous catalysis. Ways modify catalytic sites range from use reversible or irreversible adsorption molecular modifiers immobilization tethering homogeneous catalysts and development well-defined solid surfaces. The latter covers methods for dispersion single-atom within supports as well complex nanostructures, it includes post-modification materials via processes such silylation atomic layer deposition. All these methodologies exhibit both advantages limitations, but all offer new avenues design specific applications. Because high cost most fact that resulting may limited thermal chemical stability, be best aimed at improving selective synthesis value-added chemicals, incorporated organic schemes, other applications are being explored address problems energy production, instance, greener processes. details each approaches discussed, representative examples provided. We conclude some general remarks future this field.

Language: Английский

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TEMPO-Enabled Electrochemical Enantioselective Oxidative Coupling of Secondary Acyclic Amines with Ketones

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(38), P. 15599 - 15605

Published: Sept. 17, 2021

An electrochemical asymmetric coupling of secondary acyclic amines with ketones via a Shono-type oxidation has been described, affording the corresponding amino acid derivatives good to excellent diastereoselectivity and enantioselectivity. The addition an N-oxyl radical as redox mediator could selectively oxidize substrate rather than product, although their potential difference is subtle (about 13 mV). This transformation proceeds in absence stoichiometric additives, including metals, oxidants, electrolytes, which gives it functional group compatibility. Mechanistic studies suggest that proton-mediated racemization product prevented by reduction protons at cathode.

Language: Английский

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Photoelectrochemical Asymmetric Catalysis Enables Direct and Enantioselective Decarboxylative Cyanation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20201 - 20206

Published: Oct. 31, 2022

The development of efficient and sustainable methods for decarboxylative transformations is great importance due to the ease availability nontoxicity carboxylic acids. Despite tremendous efforts in this area, it remains challenging develop enantioselective direct from Herein we disclose a photoelectrocatalytic method cyanation. photoelectrochemical reactions convert acids enantioenriched nitriles by employing cerium/copper relay catalysis with cerium salt catalytic decarboxylation chiral copper complex stereoselective C-CN formation.

Language: Английский

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Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2830 - 2848

Published: Jan. 1, 2023

Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds and their mechanistic insights synthetic applications have been summarized.

Language: Английский

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Electrochemical oxidative C(sp3)–H cross-coupling with hydrogen evolution

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(3), P. 217 - 230

Published: Feb. 16, 2023

Language: Английский

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Paired Oxidative and Reductive Catalysis: Breaking the Potential Barrier of Electrochemical C(sp³)−H Alkenylation**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 1, 2023

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required enable their C(sp3 )-H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating catalysis with reductive in one cell without interference, which earth-abundant iron and nickel employed as anodic cathodic catalysts, respectively. This approach lowers previously high oxidation potential for alkane activation, enabling electrochemical functionalization at ultra-low ≈0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Language: Английский

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Dual-Catalyzed Stereodivergent Electrooxidative Homocoupling of Benzoxazolyl Acetate

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1522 - 1531

Published: Jan. 3, 2024

The development of a reliable strategy for stereodivergent radical reactions that allows convenient access to all stereoisomers homocoupling adducts with multiple stereogenic centers remains an unmet goal in organic synthesis. Herein, we describe dual-catalyzed electrooxidative C(sp3)–H/C(sp3)–H complete absolute and relative stereocontrol the synthesis molecules contiguous quaternary stereocenters general predictable manner. reaction is achieved by synergistically utilizing two distinct chiral catalysts convert identical racemic substrates into inherently distinctive reactive intermediates, dictate enantioselective addition, allow full complement stereoisomeric products via simple catalyst permutation. successful execution dual-electrocatalytic programmed activation provides significant conceptual advantage will serve as useful foundation further research cooperative stereocontrolled transformations diversity-oriented

Language: Английский

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Organic Electrosynthesis Towards Sustainability: Fundamentals and Greener Methodologies

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(9), P. 2453 - 2471

Published: May 5, 2021

Abstract The adoption of new measures that preserve our environment, on which survival depends, is a necessity. Electro‐organic processes are sustainable per se , by producing the activation substrate electron transfer at normal pressure and room temperature. In recent years, highly crescent number works organic electrosynthesis available. Novel strategies electrode being developed enabling construction great variety complex molecules. However, possibility scaled‐up mandatory in terms sustainability. Thus, some electrochemical methodologies have demonstrated to report best results reducing pollution saving energy. this personal account, these methods been compiled, organized as follows: • Direct discharge Paired reactions. Organic transformations utilizing electrocatalysis (in absence heavy metals). Selected protocols herein presented discussed with representative examples. Final perspectives reflections also considered.

Language: Английский

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Recent advances in electrochemically driven radical fluorination and fluoroalkylation

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(11), P. 2786 - 2798

Published: Jan. 1, 2021

Electrochemical fluorination (ECF) refers to the introduction of fluorine-containing moieties into organic molecules under electrochemical conditions.

Language: Английский

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