Organic Electrochemistry: Molecular Syntheses with Potential

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(3), P. 415 - 431

Published: March 9, 2021

Efficient and selective molecular syntheses are paramount to

Language: Английский

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Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

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Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

Science, Journal Year: 2021, Volume and Issue: 371(6528), P. 507 - 514

Published: Jan. 28, 2021

Vicinal dibromides and dichlorides are important commodity chemicals indispensable synthetic intermediates in modern chemistry that traditionally synthesized using hazardous elemental chlorine bromine. Meanwhile, the environmental persistence of halogenated pollutants necessitates improved approaches to accelerate their remediation. Here, we introduce an electrochemically assisted shuttle (e-shuttle) paradigm for facile scalable interconversion alkenes vicinal dihalides, a class reactions can be used both synthesize useful dihalogenated molecules from simple recycle waste material through retro-dihalogenation. The reaction is demonstrated 1,2-dibromoethane, as well 1,1,1,2-tetrachloroethane or 1,2-dichloroethane, dibrominate dichlorinate, respectively, wide range setup with inexpensive graphite electrodes. Conversely, hexachlorinated persistent pollutant lindane could fully dechlorinated benzene soil samples alkene acceptors.

Language: Английский

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Reproducibility in Electroorganic Synthesis—Myths and Misunderstandings

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(27), P. 14750 - 14759

Published: Jan. 15, 2021

The use of electric current as a traceless activator and reagent is experiencing renaissance. This sustainable synthetic method evolving into hot topic in contemporary organic chemistry. Since researchers with various scientific backgrounds are entering this interdisciplinary field, different parameters methods reported to describe the experiments. variation can lead problems reproducibility electroorganic syntheses. As an example, such density or electrode distance some cases more significant than often anticipated. Minireview provides guidelines on reporting electrosynthetic data dispels myths about technique, thereby streamlining experimental facilitate reproducibility.

Language: Английский

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Direct decarboxylative Giese reactions

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(4), P. 1415 - 1453

Published: Jan. 1, 2022

This review summarizes recent progress on using carboxylic acids directly as convenient precursors for the 1,4-radical conjugate addition (Giese) reaction.

Language: Английский

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The E factor at 30: a passion for pollution prevention

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(5), P. 1704 - 1728

Published: Jan. 1, 2023

Publication of the E Factor drew attention to problem waste in chemicals manufacture. Thirty yeas later it is abundantly clear that underlying cause global environmental problems, from climate change plastic pollution.

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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Cathodic Corrosion of Metal Electrodes—How to Prevent It in Electroorganic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(17), P. 10241 - 10270

Published: July 6, 2021

The critical aspects of the corrosion metal electrodes in cathodic reductions are covered. We discuss involved mechanisms including alloying with alkali metals, etching aqueous and aprotic media, formation hydrides organometallics. Successful approaches that have been implemented to suppress reviewed. present several examples from electroorganic synthesis where clever use alloys instead soft neat heavy metals application protective cationic additives allowed successfully exploit these materials as cathodes. Because high overpotential for hydrogen evolution reaction, such cathodes can contribute toward more sustainable green synthetic processes. reported strategies expand applications organic electrosynthesis because a negative regime is accessible within protic media common poisons, e.g., sulfur-containing substrates, compatible strongly diminished side reaction paves way efficient reductive conversions.

Language: Английский

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Electrochemical Synthesis of High-Nitrogen Materials and Energetic Materials

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(9), P. 8809 - 8840

Published: March 15, 2022

Electrochemical synthesis is a valuable method for the preparation of molecules. It innately eco-friendly, as potentially hazardous oxidation and reduction agents are replaced with electrochemical potentials. Electrochemistry commonly applied globally in numerous chemicals, but energetic materials field lags this regard. In review, we endeavor to cover entire history synthetic electrochemistry detail transformations high-nitrogen that relevant new We hope review serves starting point inform those involved chemistry, interested other applications molecules, about environmentally friendly methods available such compounds.

Language: Английский

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Counter Electrode Reactions—Important Stumbling Blocks on the Way to a Working Electro‐organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: June 7, 2022

Over the past two decades, electro-organic synthesis has gained significant interest, both in technical and academic research as well terms of applications. The omission stoichiometric oxidizers or reducing agents enables a more sustainable route for redox reactions organic chemistry. Even if it is well-known that every electrochemical oxidation only viable with an associated reduction reaction vice versa, relevance counter often less addressed. In this Review, importance corresponding highlighted how can affect performance selectivity electrolytic conversion. A selection common strategies unique concepts to tackle issue are surveyed provide guide select appropriate synthesis.

Language: Английский

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