Direct and Selective Electrocarboxylation of Styrene Oxides with CO₂ for Accessing β‐Hydroxy Acids

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(38)

Опубликована: Июль 21, 2022

Abstract Highly selective and direct electroreductive ring‐opening carboxylation of epoxides with CO 2 in an undivided cell is reported. This reaction shows broad substrate scopes within styrene oxides under mild conditions, providing practical scalable access to important synthetic intermediate β ‐hydroxy acids. Mechanistic studies show that functions not only as a carboxylative reagent this but also promoter enable efficient chemoselective transformation additive‐free electrochemical conditions. Cathodically generated α ‐radical ‐carbanion intermediates lead the regioselective formation ‐carboxylation products.

Язык: Английский

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Selective C(sp3)–H arylation/alkylation of alkanes enabled by paired electrocatalysis

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Дек. 2, 2023

We report a combination of electrocatalysis and photoredox catalysis to perform selective C(sp3)-H arylation/alkylation alkanes, in which binary catalytic system based on earth-abundant iron nickel is applied. Reaction selectivity between two-component arylation three-component alkylation tuned by modulating the applied current light source. Importantly, an ultra-low anodic potential (~0.23 V vs. Ag/AgCl) this protocol, thus enabling compatibility with variety functional groups (>70 examples). The robustness method further demonstrated preparative scale late-stage diversification natural products pharmaceutical derivatives.

Язык: Английский

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Emerging reaction technologies in pharmaceutical development: Challenges and opportunities in electrochemistry, photochemistry, and biocatalysis

Process Safety and Environmental Protection, Год журнала: 2023, Номер 192, С. 622 - 637

Опубликована: Март 3, 2023

Язык: Английский

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Deep Electroreductive Chemistry: Harnessing Carbon- and Silicon-Based Reactive Intermediates in Organic Synthesis

ACS Catalysis, Год журнала: 2023, Номер 13(12), С. 8038 - 8048

Опубликована: Май 31, 2023

ADVERTISEMENT RETURN TO ISSUEPREVViewpointNEXTDeep Electroreductive Chemistry: Harnessing Carbon- and Silicon-Based Reactive Intermediates in Organic SynthesisWen ZhangWen ZhangDepartment of Chemistry Chemical Biology, Cornell University, Ithaca, New York 14853, United StatesMore by Wen Zhanghttps://orcid.org/0000-0002-0704-3463, Weiyang GuanWeiyang GuanDepartment Guan, Jesus I. Martinez AlvaradoJesus AlvaradoDepartment Alvarado, Luiz F. T. NovaesLuiz NovaesDepartment Novaeshttps://orcid.org/0000-0003-1209-2865, Song Lin*Song LinDepartment States*Email: [email protected]More Linhttps://orcid.org/0000-0002-8880-6476Cite this: ACS Catal. 2023, 13, 12, 8038–8048Publication Date (Web):May 31, 2023Publication History Received14 March 2023Published online31 May inissue 16 June 2023https://pubs.acs.org/doi/10.1021/acscatal.3c01174https://doi.org/10.1021/acscatal.3c01174article-commentaryACS PublicationsCopyright © 2023 American Society. This publication is available under these Terms Use. Request reuse permissions free to access through this site. Learn MoreArticle Views8051Altmetric-Citations5LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated reflect usage leading up last few days.Citations number other articles citing article, calculated Crossref daily. Find more information about citation counts.The Altmetric Attention Score a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail (3 MB) Get e-AlertscloseSUBJECTS:Alkyls,Anions,Halogens,Hydrocarbons,Inorganic compounds e-Alerts

Язык: Английский

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Photoelectrochemical Fe/Ni cocatalyzed C−C functionalization of alcohols

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 19, 2024

Abstract The simultaneous activation of reactants on the anode and cathode via paired electrocatalysis has not been extensively demonstrated. This report presents a oxidative reductive catalysis based earth-abundant iron/nickel cocatalyzed C–C functionalization ubiquitous alcohols. A variety alcohols (i.e., primary, secondary, tertiary, or unstrained cyclic alcohols) can be activated at very low oxidation potential (~0.30 V vs. Ag/AgCl) photoelectrocatalysis coupled with versatile electrophiles. reactivity yields wide range structurally diverse molecules broad functional group compatibility (more than 50 examples).

Язык: Английский

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

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3309 - 3316

Опубликована: Фев. 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.

Язык: Английский

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Electroreductively Induced Radicals for Organic Synthesis

Molecules, Год журнала: 2023, Номер 28(2), С. 857 - 857

Опубликована: Янв. 15, 2023

Organic electrochemistry has attracted tremendous interest within the novel sustainable methodologies that have not only reduced undesired byproducts, but also utilized cleaner and renewable energy sources. Particularly, oxidative gained major attention. On contrary, reductive electrolysis remains an underexplored research direction. In this context, we discuss advances in transition-metal-free cathodically generated radicals for selective organic transformations since 2016. We highlight electroreductive reaction of alkyl radicals, aryl acyl silyl fluorosulfonyl trifluoromethoxyl radicals.

Язык: Английский

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Metal-free electrochemical dihydroxylation of unactivated alkenes

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 13, 2023

Herein, a metal-free electrochemical dihydroxylation of unactivated alkenes is described. The transformation proceeds smoothly under mild conditions with broad range alkenes, providing valuable and versatile dihydroxylated products in moderate to good yields without the addition costly transition metals stoichiometric amounts chemical oxidants. Moreover, this method can be applied natural pharmaceutical derivatives, further demonstrating its synthetic utility. Mechanistic studies have revealed that iodohydrin epoxide intermediate are formed during reaction process.

Язык: Английский

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Electroreductive Cross‐Electrophile Coupling of Aziridines and Aryl Bromides

Chemistry - A European Journal, Год журнала: 2023, Номер 29(36)

Опубликована: Апрель 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.

Язык: Английский

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Electrochemical Synthesis and Reactivity of Three‐Membered Strained Carbo‐ and Heterocycles

Chemistry - A European Journal, Год журнала: 2023, Номер 29(57)

Опубликована: Июль 12, 2023

Three-membered carbocyclic and heterocyclic ring structures are versatile synthetic building blocks in organic synthesis with biological importance. Moreover, the inherent strain of these three-membered rings leads to their ring-opening functionalization through C->C, C->N, C-O bond cleavage. Traditional methods for molecules require use acid catalysts or transition metals. Recently, electro-organic has emerged as a powerful tool initiating new chemical transformations. In this review, mechanistic aspects electro-mediated carbo- heterocycles highlighted.

Язык: Английский

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