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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Electrochemical Oxidation Induced Selective C–C Bond Cleavage

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(1), P. 485 - 505

Published: Oct. 5, 2020

Selective C–C bond cleavage under mild conditions can serve as a valuable tool for organic syntheses and macromolecular degradation. However, the conventional chemical methods have largely involved use of noble transition-metal catalysts well stoichiometric perhaps environmentally unfriendly oxidants, compromising overall sustainable nature transformation chemistry. In this regard, electrochemical has been identified scalable strategy that employs electricity to replace byproduct-generating reagents. To date, progress made in area mainly relied on Kolbe electrolysis related processes. Encouragingly, more examples bonds via other maneuvers recently developed. This review provides an overview most recent significant developments electrochemically oxidative selective cleavage, with emphasis both synthetic outcomes reaction mechanisms, it showcases innate advantages exciting potentials synthesis.

Language: Английский

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Synthesis and applications of sodium sulfinates (RSO₂Na): a powerful building block for the synthesis of organosulfur compounds

RSC Advances, Journal Year: 2021, Volume and Issue: 11(16), P. 9130 - 9221

Published: Jan. 1, 2021

This review provides a unique and comprehensive overview of sodium sulfinates for synthesizing many valuable sulfur-containing compounds, such as thiosulfonates, sulfonamides, sulfides, sulfones, allyl vinyl sulfones β-keto sulfones.

Language: Английский

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Recent developments in the difunctionalization of alkenes with C–N bond formation

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(18), P. 5206 - 5228

Published: Jan. 1, 2021

Various alkene difunctionalization reactions involving nitridization, diamination, azidation, oxyamination, carboamination, aminohalogenation, and nitration are introduced in this review.

Language: Английский

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Recent Progress in Sulfonylation via Radical Reaction with Sodium Sulfinates, Sulfinic Acids, Sulfonyl Chlorides or Sulfonyl Hydrazides

ChemistrySelect, Journal Year: 2020, Volume and Issue: 5(42), P. 13103 - 13134

Published: Nov. 13, 2020

Abstract Sodium sulfinates, sulfinic acids, sulfonyl chlorides and hydrazides as readily available efficient sulfonylation reagents have been extensively explored in recent years. Sulfonyl radical can be generated from these via different methods, then the could react with various substrates pathways to afford corresponding products. In this review, we will summarize progress reaction using sodium three terms of reagents, classify reactions into four types: 1. Sulfonylation sulfinates. 2. acid. 3. chlorides. 4. hydrazides.

Language: Английский

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Oxidative Sulfonylation of Multiple Carbon‐Carbon bonds with Sulfonyl Hydrazides, Sulfinic Acids and their Salts

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(21), P. 4579 - 4654

Published: Aug. 3, 2020

Abstract Oxidative coupling methodology is widely applied for the formation of carbon‐carbon and carbon‐heteroatom bonds. This review focuses on methods oxidative sulfonylation multiple bonds involving sulfonyl hydrazides, sulfinic acids their salts as reagents. Under conditions, they generate radicals, trapped by resulting in a variety SO 2 ‐containing products: mainly, vinyl alkynyl sulfones, hydroxy‐, keto, halo‐substituted sulfonylated derivatives carbo‐ heterocycles. exhaustive summarizes 321 references from 1996 to 2020 with specialization studies last five years, divided into chapters according classes compounds being sulfonylated. magnified image

Language: Английский

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Electrochemical synthesis of enaminones via a decarboxylative coupling reaction

Green Chemistry, Journal Year: 2019, Volume and Issue: 21(14), P. 3796 - 3801

Published: Jan. 1, 2019

Metal-free and oxidant-free n-Bu₄NI as a redox catalyst electrolyte.

Language: Английский

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Progress in Electrochemical Trifluoromethylation Reactions

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(23), P. 5219 - 5237

Published: Oct. 13, 2020

Abstract The importance of fluorinated organic molecules in drugs and pharmaceuticals led to the development several synthetic methods for introducing fluorine into bioactive trifluoromethylation is one key approaches same. Electrochemical synthesis has emerged as most sustainable, green strategies recent years new developments electroorganic also focus on electrochemical compounds. A considerable number reports have appeared literature this review surveys all reactions. This highly sustainable trifluoromethylating protocol will emerge further soon pave way more energy‐efficient protocols. magnified image

Language: Английский

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Small rings in the bigger picture: ring expansion of three- and four-membered rings to access larger all-carbon cyclic systems

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7513 - 7538

Published: Jan. 1, 2021

Ring-expansion of strained small-size rings to forge larger all-carbon ones, allows a rapid build-up molecular complexity.

Language: Английский

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Electrochemical Oxidative Aryl(alkyl)trifluoromethylation of Allyl Alcohols via 1,2-Migration

Organic Letters, Journal Year: 2019, Volume and Issue: 21(12), P. 4619 - 4622

Published: May 30, 2019

An electrochemical oxidative difunctionalization of allyl alcohols for the synthesis β-trifluoromethyl ketones is achieved through a 1,2-migration process. A series can be facilely obtained utilizing CF3SO2Na as radical source, eliminating use metals and sacrificial chemical oxidants. Importantly, this protocol not only realizes aryl migration but also offers alkyl-migration products. Additionally, an electrochemically catalyzed ring expansion gram-scale reaction demonstrated synthetic usefulness protocol.

Language: Английский

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