Electrophotocatalytic Reductive 1,2‐Diarylationof Alkenes with Aryl Halides and Cyanoaromatics

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(16), P. 1921 - 1930

Published: April 7, 2023

Comprehensive Summary The radical‐mediated reductive functionalization of aryl halides has been extensively studied. However, the related intermolecular 1,2‐diarylation alkenes, using as radical sources, remains unexplored. Herein, a new electrophotocatalytic alkenes is reported and cyanoaromatics to produce polyarylated alkanes. Using synergistic cathodic reduction visible‐light photoredox catalysis, various electron‐rich electron‐deficient are combined with characterize broad substrate scope, excellent functional group compatibility, selectivity this reaction. Mechanistic investigations reveal that reaction may proceed via process initiated by generation radicals from terminated radical‐radical coupling cyanoaromatic anions.

Language: Английский

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Electrochemical oxidative difunctionalization of diazo compounds with two different nucleophiles

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: March 17, 2023

With the fast development of synthetic chemistry, introduction functional group into organic molecules has attracted increasing attention. In these reactions, difunctionalization unsaturated bonds, traditionally with one nucleophile and electrophile, is a powerful strategy for chemical synthesis. this work, we develop different path electrochemical oxidative diazo compounds two nucleophiles. Under metal-free external oxidant-free conditions, series structurally diverse heteroatom-containing hardly synthesized by traditional methods (such as high-value alkoxy-substituted phenylthioacetates, α-thio, α-amino acid derivatives well α-amino, β-amino derivatives) are obtained in synthetically useful yields. addition, procedure exhibits mild reaction excellent functional-group tolerance good efficiency on large-scale Importantly, protocol also amenable to key intermediate bioactive simple practical process.

Language: Английский

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Electrochemical Difunctionalization of Alkenes

Synthesis, Journal Year: 2023, Volume and Issue: 55(18), P. 2843 - 2859

Published: Feb. 15, 2023

Abstract The electrochemical alkene difunctionalization reaction has become a powerful and sustainable tool for the efficient construction of vicinal difunctionalized structures in organic synthesis. Since only electrons are used as redox agents, avoids need additional catalysts, metal or chemical oxidants does not generate waste. Herein we summarize latest contributions alkenes over last 3–4 years. We discuss detail features, scope, limitations, mechanistic rationalizations three categories methods: (1) terminated by nucleophiles, (2) radicals, (3) functionality migration. 1 Introduction 2 Electrochemical Alkene Difunctionalization Terminated Nucleophiles 2.1 Sulfonylative Alkenes 2.2 Sulfurizative/Sulfoxidative 2.3 Azidotetrazolation 2.4 Trifluoromethylative 2.5 Diarylation 3 Radicals 3.1 Direct Radical-Coupling-Enabled 3.2 Metal-Mediated Radical Transfer Coupling Enabled 3.3 Metalloid-Mediated 4 Functionality Migration 5 Summary Outlook

Language: Английский

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Electroreduction strategy: a sustainable tool for the generation of aryl radicals

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4318 - 4342

Published: Jan. 1, 2024

This review primarily focuses on the generation of aryl radicals via an electroreduction strategy, and systematically elaborates synthetic applications, scope, limitations substrates.

Language: Английский

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Sulfoxide and Sulfone Synthesis via Electrochemical Oxidation of Sulfides

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(19), P. 13790 - 13799

Published: Sept. 22, 2021

The oxidation of diaryl sulfides and aryl alkyl to the corresponding sulfoxides sulfones under electrochemical conditions is reported. Sulfoxides are selectively obtained in good yield a constant current 5 mA for 10 h DMF, while formed as major product or 20 MeOH. oxygen both sulfoxide sulfone function derived from water.

Language: Английский

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Rapid and Mild Metal-Free Reduction of Epoxides to Primary Alcohols Mediated by HFIP

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(6), P. 3309 - 3316

Published: Feb. 25, 2022

The reduction of epoxides is a powerful tool to access anti-Markovnikov alcohols, but reported methods are poorly compatible with strongly electronically deactivated substrates. Here, we describe general method for the linear-selective styryl oxides incorporating strong electron-withdrawing groups. remains more traditional epoxide motifs, such as aliphatic and electron-rich styrene oxides. Other (hetero)cycles oxetanes, tetrahydrofurans, aziridines, cyclopropanes can also be reductively opened. This user-friendly reaction relies on combination Brønsted acid catalyst hexafluoroisopropanol solvent, thus, in contrast existing methods, it does not require anhydrous reagents or an inert atmosphere. generated primary alcohols conveniently functionalized situ by dehydrative Friedel–Crafts arylation without preactivation.

Language: Английский

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Electrochemical Syntheses of Polycyclic Aromatic Hydrocarbons (PAHs)

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(49)

Published: March 25, 2023

Polycyclic aromatic hydrocarbons (PAHs) have surfaced as increasingly viable components in optoelectronics and material sciences. The development of highly efficient atom-economic tools to prepare PAHs under exceedingly mild conditions constitutes a long-term goal. Traditional syntheses largely relied on multistep approaches or the conventional Scholl reaction. However, reactions are inefficient with electron-deficient substrates, require stoichiometric chemical oxidants, typically occur presence strong acid. In sharp contrast, electrochemistry has gained considerable momentum during past decade an alternative for facile straightforward assembly, generally via electro-oxidative dehydrogenative annulation, releasing molecular hydrogen sole byproduct by evolution This review provides overview recent significant advances field electrochemical various until January 2023.

Language: Английский

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Electroreductive Cross‐Electrophile Coupling of Aziridines and Aryl Bromides

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(36)

Published: April 18, 2023

Herein, a nickela-electrocatalyzed cross-electrophile coupling of readily available aryl aziridines and bromides under mild sustainable electrochemical conditions to access synthetic useful β-arylethylamines is developed. This protocol characterized by its exquisite chemo- regioselectivity, broad substrate scope good functional group compatibility. Mechanistic studies confirmed that the regioselectivity reactivity observed are result electro-induced ring-opening electroreductive generate benzyl radical intermediate as active species. Furthermore, this strategy also enables cross-coupling with CO2 β-amino acids conditions.

Language: Английский

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A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2500 - 2566

Published: Oct. 9, 2024

With the resurgence of electrosynthesis in organic chemistry, there is a significant increase number routes available for late-stage functionalization (LSF) drugs. Electrosynthetic methods, which obviate need hazardous chemical oxidants or reductants, offer unprecedented control reactions through continuous variation applied potential and possibility combination with photochemical processes. This capability substantial advantage performing electrochemical photoelectrochemical LSF. Ultimately, these protocols are poised to become vital component medicinal chemist's toolkit. In this review, we discuss that have been demonstrated be applicable LSF pharmaceutical drugs, their derivatives, natural substrates. We present analyze representative examples illustrate electrochemistry photoelectrochemistry valuable molecular scaffolds.

Language: Английский

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Energy-transfer-enabled photocatalytic transformations of aryl thianthrenium salts

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 8, 2024

Aryl thianthrenium salts are valuable in photocatalysis but traditionally require external electron donors for activation. This study introduces an energy transfer (EnT) strategy the activation of aryl using 2,3,4,5,6-penta(carbazol-9-yl)benzonitrile (5CzBN) as a metal-free photocatalyst, eliminating need donors. Utilizing this EnT approach, we achieve C-H deuteration arenes under visible light with CDCl

Language: Английский

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