Transition-Metal-Catalyzed C–H Alkylation Using Alkenes

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 9333 - 9403

Опубликована: Янв. 26, 2017

Alkylation reactions represent an important organic transformation to form C-C bonds. In addition conventional approaches with alkyl halides or sulfonates as alkylating agents, the use of unactivated olefins for alkylations has become attractive from both cost and sustainability viewpoints. This Review summarizes transition-metal-catalyzed various carbon-hydrogen bonds (addition C-H across olefins) using regular 1,3-dienes up May 2016. According mode activation, is divided into two sections: alkylation via activation olefin activation.

Язык: Английский

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Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

Chemical Reviews, Год журнала: 2016, Номер 117(13), С. 9163 - 9227

Опубликована: Дек. 12, 2016

The transition-metal-catalyzed addition of C–H bonds to carbonyls, imines, and related polarized π has emerged as a particularly efficient powerful approach for the construction an incredibly diverse array heteroatom-substituted products. Readily available stable inputs are typically employed, reactions often proceed with very high functional group compatibility without production waste byproducts. Additionally, many bond additions occur within cascade reaction sequences provide rapid access different heterocyclic well carbocyclic This review highlights diversity transformations that have been achieved, catalysts used, types products prepared through bonds.

Язык: Английский

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Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

Chemical Reviews, Год журнала: 2015, Номер 115(21), С. 12045 - 12090

Опубликована: Окт. 1, 2015

ADVERTISEMENT RETURN TO ISSUEPREVReviewTransition-Metal-Catalyzed Cleavage of C–N Single BondsKunbing Ouyang†‡, Wei Hao†, Wen-Xiong Zhang*†§, and Zhenfeng Xi†View Author Information† Beijing National Laboratory for Molecular Sciences (BNLMS), Key Bioorganic Chemistry Engineering the Ministry Education, College Chemistry, Peking University, 100871, China‡ Institute Chinese Academy (CAS), 100190, China§ State Elemento-Organic Nankai Tianjin 300071, China*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 21, 12045–12090Publication Date (Web):October 1, 2015Publication History Received3 July 2015Published online1 October inissue 11 November 2015https://pubs.acs.org/doi/10.1021/acs.chemrev.5b00386https://doi.org/10.1021/acs.chemrev.5b00386review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views26285Altmetric-Citations562LEARN ABOUT THESE METRICSArticle Views are COUNTER-compliant sum full text article downloads since 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated to reflect usage leading up last few days.Citations number other articles citing this article, calculated by Crossref daily. Find more information about citation counts.The Altmetric Attention Score is 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 given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Amines,Bond cleavage,Cations,Oxidative addition,Salts Get e-Alerts

Язык: Английский

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Metal–Organic Cooperative Catalysis in C–H and C–C Bond Activation

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 8977 - 9015

Опубликована: Янв. 6, 2017

Transition-metal-catalyzed activation of C-H and C-C bonds is a challenging area in synthetic organic chemistry. Among various methods to accomplish these processes, the approach using metal-organic cooperative catalytic systems one most promising. In this protocol, molecules as well transition metals act catalysts bring about reactions, which proceed with high efficiencies selectivities. Various developed for bond reactions are discussed review. Also how each catalyst affects reaction mechanism what kinds substrates can be applied processes.

Язык: Английский

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Computational Studies of Carboxylate-Assisted C–H Activation and Functionalization at Group 8–10 Transition Metal Centers

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 8649 - 8709

Опубликована: Май 22, 2017

Computational studies on carboxylate-assisted C-H activation and functionalization at group 8-10 transition metal centers are reviewed. This Review is organized by will cover work published from late 2009 until mid-2016. A brief overview of computational prior to 2010 also provided, this outlines the understanding in terms "ambiphilic metal-ligand assistance" (AMLA) "concerted metalation deprotonation" (CMD) concepts. then surveyed nature bond being activated (C(sp2)-H or C(sp3)-H), process involved (intramolecular with a directing intermolecular), context (stoichiometric within variety catalytic processes). aims emphasize connection between computation experiment highlight contribution chemistry our based activation. Some opportunities where interplay may contribute further areas applied identified.

Язык: Английский

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The Essential Role of Bond Energetics in C–H Activation/Functionalization

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 8622 - 8648

Опубликована: Март 10, 2017

The most fundamental concepts in chemistry are structure, energetics, reactivity and their inter-relationships, which indispensable for promoting into a rational science. In this regard, bond energy, the intrinsic determinant directly related to structure reactivity, should be essential serving as quantitative basis design understanding of organic transformations. Although C-H activation/functionalization have drawn tremendous research attention flourished during past decades, governing rules energetics these processes is still fragmentary seems applicable only limited cases, such metal-oxo-mediated hydrogen atom abstraction. Despite complexity difficulties measuring energies both substrates intermediates, definitely very important issue that more generally contemplated. To end, review rooted energetic aspects activation/functionalization, were previously rarely discussed detail. Starting with concise but necessary introduction various classical methods heterolytic homolytic bonds, present provides examples applied concept values energy rationalizing observations associated and/or selectivity activation/functionalization.

Язык: Английский

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High‐Valent‐Cobalt‐Catalyzed C−H Functionalization Based on Concerted Metalation–Deprotonation and Single‐Electron‐Transfer Mechanisms

ChemCatChem, Год журнала: 2016, Номер 8(7), С. 1242 - 1263

Опубликована: Март 23, 2016

Abstract C−H functionalization has been established as a powerful strategy for the commercial construction of organic molecules. This review encompasses most recent advances in activation catalyzed by earth‐abundant cobalt complexes, involving two types fundamental reaction paths, that is, concerted metalation–deprotonation (CMD) path associated with non‐oxidative and intermolecular single‐electron‐transfer (SET) path. Transformations high‐valent based on mechanisms used syntheses, including those C−C C−X (X=O N) bond formation, are herein presented.

Язык: Английский

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Metal-catalyzed C H activation/functionalization: The fundamentals

Journal of Molecular Catalysis A Chemical, Год журнала: 2016, Номер 426, С. 275 - 296

Опубликована: Сен. 9, 2016

Язык: Английский

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Nitrogen, Phosphorus, and Sulfur Co‐Doped Hollow Carbon Shell as Superior Metal‐Free Catalyst for Selective Oxidation of Aromatic Alkanes

Angewandte Chemie International Edition, Год журнала: 2016, Номер 55(12), С. 4016 - 4020

Опубликована: Фев. 17, 2016

Metal-free heteroatom-doped carbocatalysts with a high surface area are desirable for catalytic reactions. In this study, we found an efficient strategy to prepare nitrogen, phosphorus, and sulfur co-doped hollow carbon shells (denote as NPS-HCS) of 1020 m(2) g(-1). Using poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) (PZS) shell source N, P, S-doping source, the ZIF-67 core structural template well extra N-doping NPS-HCS were obtained superhydrophilicity. All these features render prepared superior metal-free carbocatalyst selective oxidation aromatic alkanes in aqueous solution. This study provides reliable facile route doped enhanced properties.

Язык: Английский

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Recent Advances in Catalytic C(sp²)–H Allylation Reactions

ACS Catalysis, Год журнала: 2017, Номер 7(4), С. 2821 - 2847

Опубликована: Март 14, 2017

The linear or branched allyl moieties on aromatic rings are well-known as ubiquitous structural motifs found in a range of natural products and medicinally relevant molecules. They also represent an important class organic intermediates for the transformation olefin group into many useful functional groups. Established methods installation allylic groups rely primarily nucleophilic substitution transmetalation aryl metal complexes to electrophiles, Lewis acid-mediated Friedel–Crafts allylation electron-rich arenes, Tsuji–Trost reactions with π-allyl species. Complementing previous protocols, transition metal-catalyzed via C–H activation strategy using various surrogates like acetates, carbonates, phosphonates, halides, alcohols, vinyl oxiranes, allenes, 1,3-dienes, others have recently emerged powerful tool creating corresponding allyl, crotyl prenyl moieties. This review, which includes all reported literature until beginning 2017, focuses recent progress direct vinylic C(sp2)–H bonds sources catalysts.

Язык: Английский

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