Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(21), P. 13230 - 13319

Published: Oct. 9, 2017

Electrochemistry represents one of the most intimate ways interacting with molecules. This review discusses advances in synthetic organic electrochemistry since 2000. Enabling methods and applications are analyzed alongside innate advantages as well future challenges electroorganic chemistry.

Language: Английский

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Electrochemical strategies for C–H functionalization and C–N bond formation

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(15), P. 5786 - 5865

Published: Jan. 1, 2018

This review provides an overview of the use electrochemistry as appealing platform for expediting carbon–hydrogen functionalization and carbon–nitrogen bond formation.

Language: Английский

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Electrochemical Arylation Reaction

Chemical Reviews, Journal Year: 2018, Volume and Issue: 118(14), P. 6706 - 6765

Published: July 2, 2018

Arylated products are found in various fields of chemistry and represent essential entities for many applications. Therefore, the formation this structural feature represents a central issue contemporary organic synthesis. By action electricity necessity leaving groups, metal catalysts, stoichiometric oxidizers, or reducing agents can be omitted part even completely. The replacement conventional reagents by sustainable not only will environmentally benign but also allows significant short cuts electrochemical In addition, methodology considered as inherently safe. current survey is organized cathodic anodic conversions well number groups being involved. some electroconversions used regenerated at electrode, whereas other electrotransformations free radical sequences exploited to afford highly process. aryl-substrate bond discussed aromatic substrates, heterocycles, multiple systems, saturated carbon substrates. This covers most seminal work advances past two decades area.

Language: Английский

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Electrochemical Oxidative Cross-coupling with Hydrogen Evolution: A Green and Sustainable Way for Bond Formation

Chem, Journal Year: 2017, Volume and Issue: 4(1), P. 27 - 45

Published: Dec. 14, 2017

Language: Английский

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Recent Advances in Oxidative R¹-H/R²-H Cross-Coupling with Hydrogen Evolution via Photo-/Electrochemistry

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(12), P. 6769 - 6787

Published: May 10, 2019

Photo-/electrochemical catalyzed oxidative R1-H/R2-H cross-coupling with hydrogen evolution has become an increasingly important issue for molecular synthesis. The dream of construction C-C/C-X bonds from readily available C-H/X-H release H2 can be facilely achieved without external chemical oxidants, providing a greener model bond formation. Given the great influence these reactions in organic chemistry, we give summary state art via photo/electrochemistry, and hope this review will stimulate development synthetic strategy near future.

Language: Английский

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Electrochemical Oxidative Cross-Coupling with Hydrogen Evolution Reactions

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 52(12), P. 3309 - 3324

Published: Nov. 27, 2019

Oxidative cross-coupling has proved to be one of the most straightforward strategies for forming carbon-carbon and carbon-heteroatom bonds from easily available precursors. Over past two decades, tremendous efforts have been devoted in this field significant advances achieved. However, order remove surplus electrons substrates chemical formation, stoichiometric oxidants are usually needed. Along with development modern sustainable chemistry, considerable perform oxidative reactions under external-oxidant-free conditions. Electrochemical synthesis is a powerful environmentally benign approach, which can not only achieve cross-couplings conditions, but also release valuable hydrogen gas during bond formation. Recently, electrochemical evolution significantly explored. This Account presents our recent toward reactions. (1) We explored thiols/thiophenols arenes, heteroarenes, alkenes C-S (2) Using strategy C-H/N-H evolution, we successfully realized C-H amination phenols, anilines, imidazopyridines, even ethers. (3) Employing halide salts as green halogenating reagents, developed clean halogenation protocol oxidation To address limitation that reaction had carry out aqueous solvent, an alternative method uses CBr4, CHBr3, CH2Br2, CCl3Br, CCl4 reagents mixture acetonitrile methanol cosolvent. (4) approach constructing C-O well-developed manner. (5) Under mild C(sp2)-H C(sp3)-H phosphonylation modest high yields. (6) achieved S-H/S-H By anodic instead oxidants, overoxidation thiols thiophenols was well avoided. (7) The methods structurally diverse heterocyclic compounds were via annulations. (8) applied difunctionalization multiple step, such C-S/C-O bonds, C-S/C-N C-Se/C-O C-Se/C-N bonds. hope studies will stimulate research interest chemists pave way discovery more

Language: Английский

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Electrocatalytic C–H Activation

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(8), P. 7086 - 7103

Published: June 18, 2018

C–H activation has emerged as a transformative tool in molecular synthesis, but until recently oxidative activations have largely involved the use of stoichiometric amounts expensive and toxic metal oxidants, compromising overall sustainable nature chemistry. In sharp contrast, electrochemical been identified more efficient strategy that exploits storable electricity place byproduct-generating chemical reagents. Thus, transition-metal catalysts were shown to enable versatile reactions manner. While palladium catalysis set stage for C(sp2)–H C(sp3)–H functionalizations by N-containing directing groups, rhodium ruthenium allowed weakly coordinating amides acids. contrast these precious 4d transition metals, recent year witnessed emergence cobalt oxygenations, nitrogenations, C–C-forming [4+2] alkyne annulations. Thereby, silver(I) oxidants was prevented, improving environmentally benign catalysis. Herein, we summarize major advances organometallic otherwise inert bonds electrocatalysis through May 2018.

Language: Английский

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An Electrocatalytic Approach to the Radical Difunctionalization of Alkenes

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(6), P. 5175 - 5187

Published: April 26, 2018

Given its many distinct characteristics, electrochemistry represents an attractive approach to meet the prevailing trends in organic synthesis. In particular, electrocatalysis—a process that integrates and small-molecule catalysis—has potential substantially improve scope of synthetic provide a wide range useful transformations. Recently, we have demonstrated new catalytic approaches combine redox-metal catalysis for oxidative difunctionalization alkenes access diverse array vicinally functionalized structures. This Perspective details our design principles underpinning development electrochemical diazidation, dichlorination, halotrifluoromethylation alkenes, which were built on foundational work by others areas electrochemistry, radical chemistry, transition-metal catalysis. The introduction redox-active Mn catalysts allows generation intermediates from readily available reagents at low potentials under mild conditions. These transition metals also impart selectivity control over alkene functionalization processes functioning as group transfer agents. As such, electrocatalytic reactions exhibit excellent chemoselectivity, broad substrate scope, high functional compatibility. Specifically, anodically coupled electrolysis, pairs two single-electron oxidation events parallel manner, enables regio- chemoselective heterodifunctionalization alkenes. products transformations describe this represent pertinent structures numerous medicinally relevant compounds. We anticipate parameters presented here are general will platform systems other challenging redox

Language: Английский

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Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2017 - 2291

Published: Nov. 23, 2021

We present here a review of the photochemical and electrochemical applications multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms which both an proton exchanged together, often concerted elementary step. As such, MS-PCET can function as non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from wide variety common functional groups. introduction practitioner’s guide reaction design, with emphasis on unique energetic selectivity features that characteristic this class. then chapters oxidative N–H, O–H, S–H, C–H homolysis methods, generation corresponding neutral species. Then, reductive PCET activations involving carbonyl, imine, other X═Y π-systems, heteroarenes, where ketyl, α-amino, heteroarene-derived radicals be generated. Finally, we asymmetric catalysis materials device applications. Within each chapter, subdivide by group undergoing homolysis, thereafter type transformation being promoted. Methods published prior end December 2020 presented.

Language: Английский

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Synthetic Photoelectrochemistry

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(29), P. 11732 - 11747

Published: Dec. 5, 2019

Photoredox catalysis (PRC) and synthetic organic electrochemistry (SOE) are often considered competing technologies in synthesis. Their fusion has been largely overlooked. We review state-of-the-art photoelectrochemistry, grouping examples into three categories: 1) electrochemically mediated photoredox (e-PRC), 2) decoupled photoelectrochemistry (dPEC), 3) interfacial (iPEC). Such synergies prove beneficial not only for "greenness" chemical selectivity, but also the accumulation of energy accessing super-oxidizing or -reducing single electron transfer (SET) agents. Opportunities challenges this emerging exciting field discussed.

Language: Английский

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