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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Electrode Materials in Modern Organic Electrochemistry

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(43), P. 18866 - 18884

Published: July 7, 2020

The choice of electrode material is critical for achieving optimal yields and selectivity in synthetic organic electrochemistry. imparts significant influence on the kinetics thermodynamics electron transfer, frequently defines success or failure a transformation. Electrode processes are complex so often empirical underlying mechanisms rationale unknown. In this review, we aim to highlight recent instances where offered, which should aid future reaction development.

Language: Английский

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New Redox Strategies in Organic Synthesis by Means of Electrochemistry and Photochemistry

ACS Central Science, Journal Year: 2020, Volume and Issue: 6(8), P. 1317 - 1340

Published: July 16, 2020

As the breadth of radical chemistry grows, new means to promote and regulate single-electron redox activities play increasingly important roles in driving modern synthetic innovation. In this regard, photochemistry electrochemistry-both considered as niche fields for decades-have seen an explosive renewal interest recent years gradually have become a cornerstone organic chemistry. Outlook article, we examine current state-of-the-art areas electrochemistry photochemistry, well nascent area electrophotochemistry. These techniques employ external stimuli activate molecules imbue privileged control reaction progress selectivity that is challenging traditional chemical methods. Thus, they provide alternative entries known reactive intermediates enable distinct strategies were previously unimaginable. Of many hallmarks, electro- are often classified "green" technologies, promoting reactions under mild conditions without necessity potent wasteful oxidants reductants. This reviews most growth these with special emphasis on conceptual advances given rise enhanced accessibility tools trade.

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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Advancing mechanochemical synthesis by combining milling with different energy sources

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 7(1), P. 51 - 65

Published: Nov. 21, 2022

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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Electrochemical Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 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.

Language: Английский

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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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Recent advances in urea- and thiourea-containing compounds: focus on innovative approaches in medicinal chemistry and organic synthesis

RSC Medicinal Chemistry, Journal Year: 2021, Volume and Issue: 12(7), P. 1046 - 1064

Published: Jan. 1, 2021

Urea and thiourea represent privileged structures in medicinal chemistry. Indeed, these moieties constitute a common framework of variety drugs bioactive compounds endowed with broad range therapeutic pharmacological properties. Herein, we provide an overview the state-of-the-art urea thiourea-containing pharmaceuticals. We also review diverse approaches pursued for (thio)urea bioisosteric replacements chemistry applications. Finally, representative examples recent advances synthesis urea- thiourea-based by enabling chemical tools are discussed.

Language: Английский

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Photoreforming of Waste Polymers for Sustainable Hydrogen Fuel and Chemicals Feedstock: Waste to Energy

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4443 - 4509

Published: April 17, 2023

Energy from renewable resources is central to environmental sustainability. Among the renewables, sunlight-driven fuel synthesis a sustainable and economical approach produce vectors such as hydrogen through water splitting. The photocatalytic splitting limited by oxidation half-reaction, which kinetically energetically demanding entails designer photocatalysts. Such challenges can be addressed employing alternative half-reactions. Photoreforming drive breakdown of waste plastics biomass into valuable organic products for production H2. We provide an overview photoreforming its underlying mechanisms that convert polymers H2 fuels fine chemicals. This paramount importance two complementary perspectives: (i) green energy harvesting (ii) sustainability decomposing valuables. Competitive results generation without hazards are being generated. process, mechanisms, critical assessment field scarce. address points focusing on concept up-to-date knowledge with key milestones achieved, uncovering concepts in photoreforming, (iii) design photocatalysts pathways use different polymer wastes substrates.

Language: Английский

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