Recent progress in cathodic reduction-enabled organic electrosynthesis: Trends, challenges, and opportunities

eScience, Journal Year: 2022, Volume and Issue: 2(3), P. 243 - 277

Published: April 23, 2022

Compared with general redox chemistry, electrochemistry using the electron as a potent, controllable, yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis. With its environmentally benign features gradually being uncovered and studied, electrosynthesis is currently undergoing revival becoming rapidly growing area within synthetic community. Among electrochemical transformations, anodically enabled ones have been far extensively exploited than those driven by cathodic reduction, although both approaches are conceptually attractive. To stimulate development of cathodically reactions, this review summarizes recently developed reductive electrosynthetic protocols, discussing highlighting reaction features, substrate scopes, applications, plausible mechanisms reveal recent trends in area. Herein, reduction-enabled preparative transformations categorized into four types: reduction (1) unsaturated hydrocarbons, (2) heteroatom-containing carbon-based systems, (3) saturated C-hetero or C–C polar/strained bonds, (4) hetero-hetero linkages. Apart from net electroreductive few examples photo-electrosynthesis well paired electrolysis also introduced, which offer opportunities overcome certain limitations improve versatility. The electrochemically driven, transition metal-catalyzed cross-couplings that comprehensively discussed several other reviews not included here.

Language: Английский

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

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(2), P. 338 - 366

Published: Jan. 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

Language: Английский

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Electrochemistry for the Chemoselective Modification of Peptides and Proteins

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(1), P. 23 - 41

Published: Dec. 30, 2021

Although electrochemical strategies for small-molecule synthesis are flourishing, this technology has yet to be fully exploited the mild and chemoselective modification of peptides proteins. With growing number diverse peptide natural products being identified emergence modified proteins as therapeutic diagnostic agents, methods stand alluring prospects harnessing reactivity polypeptides build molecular complexity. As a inherently tunable reaction platform, electrochemistry is arguably well-suited overcome chemo- regioselectivity issues which limit existing bioconjugation strategies. This Perspective will showcase recently developed approaches protein modification. The article also highlights wealth untapped opportunities production homogeneously biomolecules, with an eye toward realizing enormous potential chemistry.

Language: Английский

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Biosynthesis of polycyclopropanated high energy biofuels

Joule, Journal Year: 2022, Volume and Issue: 6(7), P. 1590 - 1605

Published: June 30, 2022

Cyclopropane-functionalized hydrocarbons are excellent fuels due their high energy density. However, the organic synthesis of these molecules is challenging. In this work, we produced polycyclopropanated fatty acids in bacteria. These can be converted into renewable for energy-demanding applications such as shipping, long-haul transport, aviation, and rocketry. We explored chemical diversity encoded thousands bacterial genomes to identify repurpose naturally occurring cyclopropanated molecules. identified a set candidate iterative polyketide synthases (iPKSs) predicted produce (POP-FAs), expressed them Streptomyces coelicolor, POP-FAs. determined structure increased production 22-fold. Finally, acid methyl esters (POP-FAMEs). Our POP fuel candidates have net heating values more than 50 MJ/L. research shows that POP-FAMEs other POPs energetic properties which sustainable alternatives scarce.

Language: Английский

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Electrophotochemical Decarboxylative Azidation of Aliphatic Carboxylic Acids

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(17), P. 10661 - 10667

Published: Aug. 16, 2022

We report an electrophotochemical metal-catalyzed strategy that harnesses the power of light and electricity for radical decarboxylative functionalization aliphatic carboxylic acids. This environmentally friendly protocol smoothly converts a diverse array acids into corresponding alkyl azides without using chemical oxidants or azido-group transfer reagents. The visible energy electric can be applied in spatially separated fashion with modular electro-flow-cell large-scale synthesis.

Language: Английский

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Kilo-Scale Electrochemical Oxidation of a Thioether to a Sulfone: A Workflow for Scaling up Electrosynthesis

Organic Process Research & Development, Journal Year: 2022, Volume and Issue: 26(8), P. 2423 - 2437

Published: July 1, 2022

Organic electrosynthesis is a rapidly evolving field, providing powerful methods to assemble targets of interest in organic synthesis. Concerns around the scalability electrochemical remain biggest reason behind their scarce implementation manufacturing routes for pharmaceutical industry. To fill this gap, we report workflow describing key reaction parameters toward successful scale-up an electrosynthetic method from milligram kilogram scale. The used demonstrate our and flow setting was oxidation thioether its corresponding sulfone, fragment active ingredient under development. use online nuclear magnetic resonance spectroscopy, offline ion chromatography, cyclic voltammetry, density functional theory calculations provided insight into mechanism side reactions.

Language: Английский

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Electrooxidative Activation of B−B Bond in B₂cat₂: Access to gem‐Diborylalkanes via Paired Electrolysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(14)

Published: Feb. 1, 2023

This report describes the unprecedented electrooxidation of a solvent (e.g., DMF)-ligated B2 cat2 complex, whereby solvent-stabilized boryl radical is formed via quasi-homolytic cleavage B-B bond in DMF-ligated cation. Cyclic voltammetry and density functional theory provide evidence to support this novel activation strategy. Furthermore, strategy for electrochemical gem-diborylation gem-bromides paired electrolysis developed first time, affording range versatile gem-diborylalkanes, which are widely used synthetic society. Notably, reaction approach scalable, transition-metal-free, requires no external activator.

Language: Английский

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Emerging reaction technologies in pharmaceutical development: Challenges and opportunities in electrochemistry, photochemistry, and biocatalysis

Process Safety and Environmental Protection, Journal Year: 2023, Volume and Issue: 192, P. 622 - 637

Published: March 3, 2023

Language: Английский

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Selective Electrochemical Modification and Degradation of Polymers

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: Feb. 28, 2024

Abstract We demonstrate that electrochemical‐induced decarboxylation enables reliable post‐polymerization modification and degradation of polymers. Polymers containing N ‐(acryloxy)phthalimides were subjected to electrochemical under mild conditions, which led the formation transient alkyl radicals. By installing these redox‐active units, we systematically modified pendent groups chain ends polyacrylates. This approach enabled production poly(ethylene‐ co ‐methyl acrylate) poly(propylene‐ copolymers, are difficult synthesize by direct polymerization. Spectroscopic chromatographic techniques reveal transformations near‐quantitative on several polymer systems. Electrochemical also all‐methacrylate poly( ‐(methacryloxy)phthalimide‐ methacrylate) copolymers with a efficiency >95 %. Chain cleavage is achieved through ‐hydroxyphthalimide ester subsequent β‐scission backbone radical. Electrochemistry thus shown be powerful tool in selective controlled macromolecular degradation.

Language: Английский

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Enhancing electrochemical reactions in organic synthesis: the impact of flow chemistry

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Utilizing electrons directly offers significant potential for advancing organic synthesis by facilitating novel reactivity and enhancing selectivity under mild conditions. As a result, an increasing number of chemists are exploring electrosynthesis. However, the efficacy electrochemical transformations depends critically on design cell. Batch cells often suffer from limitations such as large inter-electrode distances poor mass transfer, making flow promising alternative. Implementing cells, however, requires foundational understanding microreactor technology. In this review, we briefly outline applications electrosynthesis before providing comprehensive examination existing reactor technologies. Our goal is to equip with insights needed tailor their meet specific requirements effectively. We also highlight application designs in scaling up processes integrating high-throughput experimentation automation. These advancements not only enhance synthetic community but hold promise both academia industry.

Language: Английский

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