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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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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Recent Advances in the Electrochemical Synthesis of Organosulfur Compounds

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(9), P. 2526 - 2537

Published: May 7, 2021

Abstract Organosulfur compounds are being widely used in medicinal chemistry, as well organic transformations and synthetic applications. Because of their interest many areas, the development sustainable green methods to access various organosulfur has a high influence on chemistry community. Electroorganic synthesis become very valuable methodology for during last decade. The use electrochemical technology offers green, safe alternative prepare modify such compounds. This review summarises recent developments preparation sulfoxides, sulfones, sulfinic esters, sulfonamides, thiosulfonates, sulfonyl fluorides sulfoximines under reaction conditions.

Language: Английский

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Electrosynthesis of CF₃‐Substituted Polycyclic Quinazolinones via Cascade Trifluoromethylation/Cyclization of Unactivated Alkene

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(7), P. 1319 - 1325

Published: Feb. 23, 2022

Abstract An atom and step economy cascade trifluoromethylation/cyclization of unactivated alkene with Langlois reagent as a CF 3 source is described. A variety polycyclic quinazolinones were successfully synthesized in 52–81% yields under transition metal‐ oxidant‐free conditions. The used this strategy possesses the advantages bench‐stablity, cost‐effectivity high‐efficiency. Additionally, gram‐scale reaction, broad substrate scope good functional group tolerance demonstrated synthetic usefulness protocol. magnified image

Language: Английский

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Electrochemical Oxidative C–H Arylation of Quinoxalin(on)es with Arylhydrazine Hydrochlorides under Mild Conditions

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(7), P. 4764 - 4776

Published: March 23, 2022

A practical and scalable protocol for electrochemical arylation of quinoxalin(on)es with arylhydrazine hydrochlorides under mild conditions has been developed. This method exhibits high efficiency, easy scalability, broad functional group tolerance. Various arylhydrazines underwent this transformation smoothly in an undivided cell, providing the corresponding aryl-substituted moderate to good yields. radical mechanism is involved reaction.

Language: Английский

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Divergent electrolysis for the controllable coupling of thiols with 1,2-dichloroethane: a mild approach to sulfide and sulfoxide

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(3), P. 1342 - 1349

Published: Jan. 1, 2022

Electrocatalysis for the controllable coupling of thiols with DCE was achieved to generate value-added β-chloro-tethered sulfur compounds in batch and flow.

Language: Английский

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Electrochemical multi-component reaction of potassium metabisulfite with alkenes and alcohols enabling synthesis of sulfonate esters

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(16), P. 6113 - 6118

Published: Jan. 1, 2022

An electrochemical sulfur dioxide insertion reaction of alkenes and alcohols with potassium metabisulfite as the surrogate has been developed, which provides a green efficient method for preparation sulfonate esters.

Language: Английский

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Electrochemically mediated three-component synthesis of isothioureas using thiols as sulfur source

Green Synthesis and Catalysis, Journal Year: 2022, Volume and Issue: 4(1), P. 41 - 45

Published: March 4, 2022

The simultaneous binding/dissociation of multiple bonds in a one-pot manner by multicomponent reactions provide an important approach for developing novel and sustainable pathway the drug discovery process. Herein we develop electrocatalytic three-component reaction to construct multifunctional valuable isothiourea compounds, which uses thiols, isocyanides amines as substrates. Compared with previous work, organic electrosynthesis technique can avoid requirement heavy metal catalysts stoichiometric oxidants. In addition, using thiol substrate participate broadens source sulfur, also more abundant derivatives.

Language: Английский

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Ruthenium-Catalyzed Electrochemical Synthesis of Indolines through Dehydrogenative [3 + 2] Annulation with H₂ Evolution

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(21), P. 13735 - 13746

Published: Oct. 13, 2020

A dehydrogenative [3 + 2] annulation reaction of aniline derivatives and alkenes has been developed via the ruthenium-electron catalytic systems for synthesis versatile indolines. Electricity is used as a sustainable oxidant to regenerate active Ru(II) catalyst promote H2 evolution. This protocol ecofriendly easy handle it uses simple undivided cell in mild conditions without employment metal oxidants.

Language: Английский

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Recyclable and reusablen-Bu₄NBF₄/PEG-400/H₂O system for electrochemical C-3 formylation of indoles with Me₃N as a carbonyl source

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(11), P. 4107 - 4113

Published: Jan. 1, 2021

An eco-friendly electrochemical C-3 formylation of indoles using Me₃N as a carbonyl donor in recyclable reaction medium has been developed.

Language: Английский

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