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

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2487 - 2649

Опубликована: Ноя. 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.

Язык: Английский

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Synthetic Molecular Photoelectrochemistry: New Frontiers in Synthetic Applications, Mechanistic Insights and Scalability

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(12)

Опубликована: Сен. 3, 2021

Synthetic photoelectrochemistry (PEC) is receiving increasing attention as a new frontier for the generation and handling of reactive intermediates. PEC permits selective single-electron transfer (SET) reactions in much greener way broadens redox window possible transformations. Herein, most recent contributions are reviewed, demonstrating exciting opportunities, namely, combination with other reactivity paradigms (hydrogen-atom transfer, radical polar crossover, energy sensitization), scalability up to multigram scale, novel selectivities SET super-oxidations/reductions importance precomplexation temporally enable excited ion catalysis.

Язык: Английский

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Electrochemical Late-Stage Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11269 - 11335

Опубликована: Сен. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Язык: Английский

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

eScience, Год журнала: 2022, Номер 2(3), С. 243 - 277

Опубликована: Апрель 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.

Язык: Английский

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Overcoming the limitations of Kolbe coupling with waveform-controlled electrosynthesis

Science, Год журнала: 2023, Номер 380(6640), С. 81 - 87

Опубликована: Апрель 6, 2023

The Kolbe reaction forms carbon-carbon bonds through electrochemical decarboxylative coupling. Despite more than a century of study, the has seen limited applications owing to extremely poor chemoselectivity and reliance on precious metal electrodes. In this work, we present simple solution long-standing challenge: Switching potential waveform from classical direct current rapid alternating polarity renders various functional groups compatible enables sustainable carbon-based electrodes (amorphous carbon). This breakthrough enabled access valuable molecules that range useful unnatural amino acids promising polymer building blocks readily available carboxylic acids, including biomass-derived acids. Preliminary mechanistic studies implicate role in modulating local pH around crucial acetone as an unconventional solvent for reaction.

Язык: Английский

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Chemoselective (Hetero)Arene Electroreduction Enabled by Rapid Alternating Polarity

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(13), С. 5762 - 5768

Опубликована: Март 29, 2022

Conventional chemical and even electrochemical Birch-type reductions suffer from a lack of chemoselectivity due to reliance on alkali metals or harshly reducing conditions. This study reveals that simpler avenue is available for such by simply altering the waveform current delivery, namely rapid alternating polarity (rAP). The developed method solves these issues, proceeding in protic solvent, can be easily scaled up without any metal additives stringently anhydrous

Язык: Английский

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E3 ligase ligand chemistries: from building blocks to protein degraders

Chemical Society Reviews, Год журнала: 2022, Номер 51(9), С. 3487 - 3534

Опубликована: Янв. 1, 2022

This review comprehensively illustrates chemistries of E3 ligase ligands, which were used successfully in the development PROTACs.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(47)

Опубликована: Июнь 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.

Язык: Английский

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Asymmetric-waveform alternating current-promoted silver catalysis for C–H phosphorylation

Nature Synthesis, Год журнала: 2023, Номер 2(2), С. 172 - 181

Опубликована: Янв. 5, 2023

Язык: Английский

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Advancing Strategies for Proteolysis-Targeting Chimera Design

Journal of Medicinal Chemistry, Год журнала: 2023, Номер 66(4), С. 2308 - 2329

Опубликована: Фев. 14, 2023

Proteolysis-targeting chimeras (PROTACs) have shown great therapeutic potential by degrading various disease-causing proteins, particularly those related to tumors. Therefore, the introduction of PROTACs has ushered in a new chapter antitumor drug development, marked significant advances over recent years. Herein, we describe developments PROTAC technology, focusing on design strategy, development workflow, and future outlooks. We also discuss opportunities challenges for research.

Язык: Английский

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