A molecular mediator for reductive concerted proton-electron transfers via electrocatalysis

Chalkley, Matthew J.; Garrido‐Barros, Pablo; Peters, Jonas C.

doi:10.1126/science.abc1607

Cited by 131 publications

(176 citation statements)

References 56 publications

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“…Regarding the redox catalyst nature, diverse species have been used during the last decades: metals in fundamental state or in ionic form, [86] organometallic complexes, [87] halogens [88] or organic molecules, [89] which should be selectively chosen to produce a particular organic transformation. Some of the first described electrocatalytic reactions employed chromium (VI) salts, generated at the anode, to oxidize the side chains of arenes [86e] .…”

Section: Even More Sustainable Electrosynthesesmentioning

confidence: 99%

Organic Electrosynthesis Towards Sustainability: Fundamentals and Greener Methodologies

Cembellín

Batanero

2021

The Chemical Record

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

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Section: Even More Sustainable Electrosynthesesmentioning

confidence: 99%

Organic Electrosynthesis Towards Sustainability: Fundamentals and Greener Methodologies

Cembellín

Batanero

2021

The Chemical Record

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“…Rational design of a strong CPET donor for electrocatalytic reduction of carbonyl species by decoupling ET and PT sites. [37] Electrocatalytic alcohol oxidation. The reverse process, i.e.…”

Section: Beyond Small Molecule Activation: Carbonyl Reduction Alcohol Oxidationmentioning

confidence: 99%

“…Besides the possibility to use hydride transfer pathways (see above), Peters et al. recently achieved electrocatalytic concerted proton‐electron transfer (eCPET) strategies for carbonyl reduction [37] . Similar approaches have already been investigated for the reverse reaction, i. e. the oxidation of alcohols using electrocatalytic HAT‐systems based on nitroxyl‐radicals (for a discussion of HAT vs. CPET see e. g. ref [38]) [38–39] .…”

Section: Reducing and Cleaving Bonds With Electrons And Protonsmentioning

confidence: 99%

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Taming Electron Transfers: From Breaking Bonds to Creating Molecules

Wolff

Robert

2021

The Chemical Record

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The electron is the ultimate redox reagent to build and reshape molecular structures. Understanding and controlling the parameters underlying dissociative electron transfer (DET) reactivity and its coupling with proton transfer is crucial for combining selectivity, kinetics and energy efficiency in molecular chemistry. Reactivity understanding and mechanistic elements in DET processes are traced back and key examples of current research efforts are presented, demonstrating a large variety of applications. The involvement of DET pathways indeed encompasses a broad range of processes such as photoredox catalysis, CO2 reduction and alcohol oxidation. Interplay between these experimental examples and fundamental mechanistic study provides a powerful path to the understanding of driving force-rate relationships, which is crucial for the development of future generations of energy efficient catalytic schemes in redox organic chemistry.

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“…The studies outlined above enable us to draw on these concepts to affect product selectivity for electroorganic transformations. For comparison, the selectivity of a simple, but nevertheless instructive, electrochemical reduction of ketones is examined, which has also been recently utilized as a model PCET reaction to describe the efficacy of new homogeneous PCET mediator‐based strategies 70 . The pH‐dependent pinacol versus alcohol product selectivity observed in the reduction of phenyl ketones, 4 , is a well‐documented phenomenon and extensive mechanistic studies have been conducted over several decades ago 48,71–73 .…”

Section: Introductionmentioning

confidence: 99%

The interface is a tunable dimension in electricity‐driven organic synthesis

Wuttig

Toste

2021

Natural Sciences

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Predictive control over the selectivity outcome of an organic synthetic method is an essential hallmark of reaction success. Electricity‐driven synthesis offers a reemerging approach to facilitate the design of reaction sequences toward increased molecular complexity. In addition to the desirable sustainability features of electroorganic processes, the inherent interfacial nature of electrochemical systems present unique opportunities to tune reaction selectivity. To illustrate this feature, we outline examples of mechanism‐guided interfacial control over CO2 electroreduction selectivity; a well‐studied and instructive electrochemical process with multiple reduction products that are thermodynamically accessible. These studies reveal how controlled proton delivery to the electrode surface and substrate electrosorption with the electrode dictate reaction selectivity. We describe and compare simple, yet salient, examples from the electroorganic literature, where we postulate that similar effects predominate the observed reactivity. This perspective highlights how the interface serves as a tunable dimension in electrochemical processes and delineates unique tools to study, manipulate, and achieve reaction selectivity in electricity‐driven organic synthesis. KEY POINTS Electricity‐driven synthesis enables chemical and industrial communities to contribute to sustainability goals. Electricity‐driven processes occur at phase boundaries, thus unveiling their molecular‐level roadmaps involves the synergistic study of materials, interfacial, and molecular science. Bridging concepts that transcend the topical nature of two electricity‐driven processes—CO2 reduction and electroorganic synthesis—reveals tools to manipulate reaction selectivity.

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A molecular mediator for reductive concerted proton-electron transfers via electrocatalysis

Cited by 131 publications

References 56 publications

Organic Electrosynthesis Towards Sustainability: Fundamentals and Greener Methodologies

Organic Electrosynthesis Towards Sustainability: Fundamentals and Greener Methodologies

Taming Electron Transfers: From Breaking Bonds to Creating Molecules

The interface is a tunable dimension in electricity‐driven organic synthesis

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