Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Июнь 16, 2023

Abstract Electrochemistry utilizes electrons as a potent, controllable, and traceless alternative to chemical oxidants or reductants, typically offers more sustainable option for achieving selective organic synthesis. Recently, the merger of electrochemistry with readily available electrophiles has been recognized viable increasingly popular methodology efficiently constructing challenging C−C C‐heteroatom bonds in manner complex molecules. In this mini‐review, we have systematically summarized most recent advances electroreductive cross‐electrophile coupling (eXEC) reactions during last decade. Our focus on electrophiles, including aryl alkyl (pseudo)halides, well small molecules such CO 2 , SO D O.

Язык: Английский

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Ni-Electrocatalytic Enantioselective Doubly Decarboxylative C(sp³)–C(sp³) Cross Coupling

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(21), С. 11518 - 11523

Опубликована: Май 16, 2023

The first examples of enantioselective doubly decarboxylative cross coupling are disclosed. Malonate half amides smoothly coupled to a variety primary carboxylic acids after formation the corresponding redox-active esters under Ni-electrocatalytic conditions using new chiral ligand based on PyBox, resulting in with α-alkylated stereocenters. scope reaction is broad, tolerating numerous functional groups, and uniformly proceeds high ee. Finally, potential utility this radical–radical reductive simplify synthesis demonstrated case studies.

Язык: Английский

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Mechanistic Investigation of Ni-Catalyzed Reductive Cross-Coupling of Alkenyl and Benzyl Electrophiles

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(27), С. 14705 - 14715

Опубликована: Июнь 26, 2023

Mechanistic investigations of the Ni-catalyzed asymmetric reductive alkenylation

Язык: Английский

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Enantioselective C(sp²)–C(sp³) Bond Construction by Ni Catalysis

Accounts of Chemical Research, Год журнала: 2024, Номер 57(5), С. 751 - 762

Опубликована: Фев. 12, 2024

ConspectusAfter decades of palladium dominating the realm transition-metal-catalyzed cross-coupling, recent years have witnessed exciting advances in development new nickel-catalyzed cross-coupling reactions to form C(sp3) centers. Nickel possesses distinct properties compared with palladium, such as facile single-electron transfer electrophiles and rapid C–C reductive elimination from NiIII. These properties, among others, make nickel particularly well-suited for (RCC) which two are coupled an exogenous reductant is used turn over metal catalyst. Ni-catalyzed RCCs use readily available stable starting materials exhibit good functional group tolerance, makes them appealing applications synthesis complex molecules. Building upon foundational work by groups Kumada, Durandetti, Weix, well advancements enantioselective redox-neutral cross-couplings led Fu co-workers, we initiated a program explore feasibility developing highly RCCs. Our research has also been driven keen interest unraveling factors contributing enantioinduction electrophile activation seek avenues advancing our understanding further these reactions.In first part this Account, organize reported methods on basis identity electrophiles, including benzylic chlorides, N-hydroxyphthalimide (NHP) esters, α-chloro esters nitriles. We highlight how selection specific chiral ligands plays pivotal role achieving high cross-selectivity enantioselectivity. In addition, show that reduction can be accomplished not only heterogeneous reductants, Mn0, but soluble organic tetrakis(dimethylamino)ethylene (TDAE), electrochemically. The homogeneous TDAE, suited studying mechanism transformation. Although Account primarily focuses RCCs, using trifluoroborate (BF3K) salts radical precursors dual-Ni/photoredox systems.At end summarize relevant mechanistic studies closely related asymmetric alkenylation developed laboratory provide context between others. discuss ligand influence rates mechanisms mode generation optimize yield RCC. endeavors offer insights intricate at play goal rate improve substrate scope anticipate share guidance field.

Язык: Английский

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Dual-Catalyzed Stereodivergent Electrooxidative Homocoupling of Benzoxazolyl Acetate

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1522 - 1531

Опубликована: Янв. 3, 2024

The development of a reliable strategy for stereodivergent radical reactions that allows convenient access to all stereoisomers homocoupling adducts with multiple stereogenic centers remains an unmet goal in organic synthesis. Herein, we describe dual-catalyzed electrooxidative C(sp3)–H/C(sp3)–H complete absolute and relative stereocontrol the synthesis molecules contiguous quaternary stereocenters general predictable manner. reaction is achieved by synergistically utilizing two distinct chiral catalysts convert identical racemic substrates into inherently distinctive reactive intermediates, dictate enantioselective addition, allow full complement stereoisomeric products via simple catalyst permutation. successful execution dual-electrocatalytic programmed activation provides significant conceptual advantage will serve as useful foundation further research cooperative stereocontrolled transformations diversity-oriented

Язык: Английский

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Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Язык: Английский

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Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES)

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 19, 2025

ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with transition metal catalysis. On one hand, we have rationalized that compounds can serve as molecular electrocatalysts (mediators) reduce overpotentials and enhance both reactivity selectivity reactions. other conditions for catalysis be substantially improved through electrochemistry, enabling precise modulation metal's oxidation state by controlling potentials regulating electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional catalysis, particularly those related use redox-active chemical reagents. Furthermore, redox conveniently tuned modifying their ligands, thereby governing reaction regioselectivity stereoselectivity. As a result, AOES emerged powerful promising tool chiral compounds.In this Account, summarize contextualize efforts AOES. Our primary strategy involves leveraging controllability potential regulate organometallics, facilitating desired An efficient platform was established under mild conditions, significantly reducing reliance on been systematically categorized into three sections based distinct electrolysis modes: combined anodic oxidation, cathodic reduction, paired electrolysis. In each section, highlight innovative discoveries tailored unique characteristics respective modes.In many transformations, metal-catalyzed reactions involving reagents utilizing exhibit similar reactivities. However, also observed notable differences certain cases. These findings include following: (1) Enhanced efficiency synthesis: instance, Rh-catalyzed enantioselective functionalization C–H bonds demonstrates superior efficiency. (2) Expanded scope transformations: previously challenging achieved due tunability potentials. A example is reductive coupling aryl chlorides, expands range accessible transformations. Additionally, mechanistic studies explore techniques intrinsic such controlled experiments, impact electrode materials catalyst performance, cyclic voltammetry studies. investigations provide more intuitive understanding behavior catalysts study mechanisms, guide design new catalytic systems.The advancements offer robust environmentally friendly sustainable selective By integrating developed versatile organic not only enhances but reduces environmental impact. We anticipate Account will stimulate further innovation realm AOES, leading discovery systems development synthetic methodologies.

Язык: Английский

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Enantioselective Reductive Cross-Couplings of Olefins by Merging Electrochemistry with Nickel Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(44), С. 23910 - 23917

Опубликована: Окт. 26, 2023

The merger of electrochemistry and transition metal catalysis has emerged as a powerful tool to join two electrophiles in an enantioselective manner. However, the development electroreductive cross-couplings olefins remains challenge. Inspired by advantages synergistic use with nickel catalysis, we present here Ni-catalyzed cross-coupling acrylates aryl halides alkyl bromides, which affords chiral α-aryl carbonyls good excellent enantioselectivity. Additionally, this catalytic reaction can be applied (hetero)aryl chlorides, is difficult achieve other methods. combination cyclic voltammetry analysis electrode potential studies suggests that NiI species activates oxidative addition bromides single-electron transfer.

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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Asymmetric Paired Electrocatalysis: Enantioselective Olefin–Sulfonylimine Coupling

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(3), С. 1984 - 1991

Опубликована: Дек. 19, 2023

Asymmetric electrocatalysis offers exciting new strategies for the synthesis of chiral molecules through novel reaction pathways. However, simultaneous activation reactants on both electrodes via asymmetric paired electrolysis, which is more energy efficient and economic than single half-electrode synthesis, remains a formidable challenge. Herein, an olefin–sulfonylimine coupling presented first time. In this protocol, Co-catalyzed hydrogen atom transfer anode Ni-catalyzed sulfonylimine reduction cathode were seamlessly cross-coupled. The catalytic system enables formation amine products bearing tetrasubstituted carbon stereocenter with high enantioselectivity (up to 96% ee).

Язык: Английский

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