A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

Chemical Society Reviews, Год журнала: 2018, Номер 47(17), С. 6603 - 6743

Опубликована: Янв. 1, 2018

The present review is devoted to summarizing the recent advances (2015-2017) in field of metal-catalysed group-directed C-H functionalisation. In order clearly showcase molecular diversity that can now be accessed by means directed functionalisation, whole organized following directing groups installed on a substrate. Its aim comprehensive reference work, where specific group easily found, together with transformations which have been carried out it. Hence, primary format this schemes accompanied concise explanatory text, are ordered sections according their chemical structure. feature typical substrates used, products obtained as well required reaction conditions. Importantly, each example commented respect most important positive features and drawbacks, aspects such selectivity, substrate scope, conditions, removal, greenness. targeted readership both experts functionalisation chemistry (to provide overview progress made last years) and, even more so, all organic chemists who want introduce way thinking for design straightforward, efficient step-economic synthetic routes towards molecules interest them. Accordingly, should particular also scientists from industrial R&D sector. overall goal promote application reactions outside research dedicated method development establishing it valuable archetype contemporary R&D, comparable role cross-coupling play date.

Язык: Английский

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Transition metal-catalyzed C–H bond functionalizations by the use of diverse directing groups

Organic Chemistry Frontiers, Год журнала: 2015, Номер 2(9), С. 1107 - 1295

Опубликована: Янв. 1, 2015

In this review, a summary of transition metal-catalyzed C–H activation by utilizing the functionalities as directing groups is presented.

Язык: Английский

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Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

Accounts of Chemical Research, Год журнала: 2015, Номер 48(4), С. 1053 - 1064

Опубликована: Март 10, 2015

ConspectusIn recent years, carbon–hydrogen bond functionalization has evolved from an organometallic curiosity to a tool used in mainstream applications the synthesis of complex natural products and drugs. The use C–H bonds as transformable functional group is advantageous because these are most abundant functionality organic molecules. One-step conversion desired shortens synthetic pathways, saving reagents, solvents, labor. Less chemical waste generated well, showing that this chemistry environmentally beneficial. This Account describes development bidentate, monoanionic auxiliaries for transition-metal-catalyzed reactions. was initially developed overcome limitations with palladium-catalyzed assisted by monodentate directing groups. By electron-rich bidentate groups, unactivated sp3 under palladium catalysis been developed. Furthermore, number base-metal complexes catalyze sp2 bonds. At point, aminoquinoline, picolinic acid, related compounds among versatile moieties chemistry. These groups facilitate catalytic iron, cobalt, nickel, copper, ruthenium, rhodium, complexes. Exceptionally general reactivity observed, enabling, other transformations, direct arylation, alkylation, fluorination, sulfenylation, amination, etherification, carbonylation, alkenylation versatility auxilaries can be attributed following factors. First, they capable stabilizing high oxidation states transition metals, thereby facilitating step. Second, removed, enabling their medicinally relevant substances. While presents significant advance, several methodology apparent. expensive second-row metal catalysts still required efficient functionalization. need install subsequently remove relatively disadvantage.

Язык: Английский

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Substrate Activation Strategies in Rhodium(III)-Catalyzed Selective Functionalization of Arenes

Accounts of Chemical Research, Год журнала: 2015, Номер 48(4), С. 1007 - 1020

Опубликована: Апрель 6, 2015

The possibility of developing new methods for the efficient construction organic molecules via disconnections other than traditional functional group transformations has driven interest in direct functionalization C-H bonds. ubiquity bonds makes such attractive, but they also pose several challenges. first is reactivity and selectivity To achieve this, directing groups (DGs) are often installed that can enhance effective concentration catalyst, leading to thermodynamically stable metallacyclic intermediates. However, presence a pendant product undesirable unnecessary. This may account limitation applications reactions more common general uses. Thus, development removable or functionalizable desirable. Another key problem resulting M-C bond be low, which limit scope coupling partners hence reaction patterns activation reactions. While Cp*Rh(III)-catalyzed arenes was reported only 7 years ago, significant progress been made this area past few years. We began our studies 2010, we others have demonstrated diversified catalytic realized using Cp*Rh(III) complexes with high reactivity, stability, compatibility. Account describes efforts solve some these challenges Rh(III) catalysis. fulfilled design arene substrates by taking advantage nucleophilicity, electrophilicity, oxidizing potential, properties participating ligand when coupled relatively reactive unsaturated as alkenes alkynes. These situ funtionalizable roles DG allowed extensive chemical manipulation initial product, especially diverse array heterocycles. In polar partners, Rh(III)-C(aryl) showed higher both an organometallic reagent nucleophilic aryl source. were accordingly activated virtue umpolung, ring strain, rearomatization. All possible integration compatibility Rh(III)-C into systems. date achieved under rhodium addition, means stoichiometric reactions, gained mechanistic insights interactions between Rh-C opened avenues future

Язык: Английский

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Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Chemical Reviews, Год журнала: 2020, Номер 120(3), С. 1788 - 1887

Опубликована: Янв. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

Язык: Английский

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Photoredox-Catalyzed C–H Functionalization Reactions

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1925 - 2016

Опубликована: Сен. 29, 2021

The fields of C–H functionalization and photoredox catalysis have garnered enormous interest utility in the past several decades. Many different scientific disciplines relied on strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, fine chemical synthesis. In this Review, we highlight use reactions. We separate review into inorganic/organometallic catalysts organic-based catalytic systems. Further subdivision by reaction class─either sp2 or sp3 functionalization─lends perspective tactical for these methods synthetic applications.

Язык: Английский

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Recent Advances in C–H Functionalization

The Journal of Organic Chemistry, Год журнала: 2016, Номер 81(2), С. 343 - 350

Опубликована: Янв. 15, 2016

ADVERTISEMENT RETURN TO ISSUEEditorialNEXTRecent Advances in C–H FunctionalizationHuw M. L. Davies and Daniel MortonView Author Information Department of Chemistry, Emory UniversityCite this: J. Org. Chem. 2016, 81, 2, 343–350Publication Date (Web):January 15, 2016Publication History Published online15 January 2016Published inissue 15 2016https://pubs.acs.org/doi/10.1021/acs.joc.5b02818https://doi.org/10.1021/acs.joc.5b02818editorialACS PublicationsCopyright © 2016 American Chemical Society. This publication is available under these Terms Use. Request reuse permissions free to access through this site. Learn MoreArticle Views42947Altmetric-Citations516LEARN 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 by 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 (2 MB) Get e-AlertscloseSUBJECTS:Aromatic compounds,Catalysts,Chemical reactions,Functionalization,Selectivity 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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Key Green Chemistry research areas from a pharmaceutical manufacturers’ perspective revisited

Green Chemistry, Год журнала: 2018, Номер 20(22), С. 5082 - 5103

Опубликована: Янв. 1, 2018

The ACS Green Chemistry Institute® Pharmaceutical Roundtable has assembled an updated list of key research areas to highlight transformations and reaction media where more sustainable technologies would be most impactful.

Язык: Английский

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