Electrochemical Oxidative Cross-Coupling with Hydrogen Evolution Reactions

Accounts of Chemical Research, Год журнала: 2019, Номер 52(12), С. 3309 - 3324

Опубликована: Ноя. 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

Язык: Английский

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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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Recent advances in electrochemical oxidative cross-coupling with hydrogen evolution involving radicals

Chemical Society Reviews, Год журнала: 2021, Номер 50(18), С. 10058 - 10086

Опубликована: Янв. 1, 2021

This tutorial review provides an overview of the most recent developments in electrochemical oxidative cross-coupling with hydrogen evolution involving radicals.

Язык: Английский

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

RSC Advances, Год журнала: 2021, Номер 11(16), С. 9130 - 9221

Опубликована: Янв. 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.

Язык: Английский

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Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions

Green Chemistry, Год журнала: 2019, Номер 22(2), С. 433 - 438

Опубликована: Ноя. 26, 2019

The first example of selective oxidation sulfides to sulfones and sulfoxides using molecular oxygen under clean conditions was established. desired products could be easily collected through recrystallization in large-scale preparation.

Язык: Английский

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Visible-light photoredox-catalyzed dual C–C bond cleavage: synthesis of 2-cyanoalkylsulfonylated 3,4-dihydronaphthalenes through the insertion of sulfur dioxide

Chemical Communications, Год журнала: 2020, Номер 56(20), С. 3011 - 3014

Опубликована: Янв. 1, 2020

An efficient novel visible-light photoredox-catalyzed dual carbon-carbon bond cleavage of methylenecyclopropanes and cycloketone oximes for the synthesis 2-cyanoalkylsulfonated 3,4-dihydronaphthalenes through insertion sulfur dioxide is established. This bonds involves a radical pathway goes sequence iminyl formation, cleavage, insertion, sulfonyl addition, another intramolecular cyclization.

Язык: Английский

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

ChemistrySelect, Год журнала: 2020, Номер 5(42), С. 13103 - 13134

Опубликована: Ноя. 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.

Язык: Английский

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

Advanced Synthesis & Catalysis, Год журнала: 2020, Номер 362(21), С. 4579 - 4654

Опубликована: Авг. 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

Язык: Английский

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Recent Progress and Emerging Technologies towards a Sustainable Synthesis of Sulfones

ChemSusChem, Год журнала: 2021, Номер 14(22), С. 4878 - 4902

Опубликована: Сен. 3, 2021

Sulfones play a pivotal role in modern organic chemistry. They are highly versatile building blocks and find various applications as drugs, agrochemicals, or functional materials. Therefore, sustainable access to this class of molecules is great interest. Herein, the goal was provide summary on recent developments field sulfone synthesis. Advances existing limitations traditional approaches towards sulfones were reviewed selected examples. Furthermore, novel emerging technologies for more synthesis future directions discussed.

Язык: Английский

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Recent advances in photoelectrochemical cells (PECs) for organic synthesis

Organic Chemistry Frontiers, Год журнала: 2020, Номер 7(14), С. 1895 - 1902

Опубликована: Янв. 1, 2020

The application of PECs in organic synthesis reactions and their reaction mechanisms are highlighted.

Язык: Английский

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