3d Transition Metals for C–H Activation

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Language: Английский

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Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 9247 - 9301

Published: Jan. 4, 2017

Catalytic transformation of ubiquitous C-H bonds into valuable C-N offers an efficient synthetic approach to construct N-functionalized molecules. Over the last few decades, transition metal catalysis has been repeatedly proven be a powerful tool for direct conversion cheap hydrocarbons synthetically versatile amino-containing compounds. This Review comprehensively highlights recent advances in intra- and intermolecular amination reactions utilizing late metal-based catalysts. Initial discovery, mechanistic study, additional applications were categorized on basis scaffolds types reactions. Reactivity selectivity novel systems are discussed three sections, with each being defined by proposed working mode.

Language: Английский

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Palladium-Catalyzed Transformations of Alkyl C–H Bonds

Chemical Reviews, Journal Year: 2016, Volume and Issue: 117(13), P. 8754 - 8786

Published: Dec. 2, 2016

This Review summarizes the advancements in Pd-catalyzed C(sp3)-H activation via various redox manifolds, including Pd(0)/Pd(II), Pd(II)/Pd(IV), and Pd(II)/Pd(0). While few examples have been reported of alkane C-H bonds, many activation/C-C C-heteroatom bond forming reactions developed by use directing group strategies to control regioselectivity build structural patterns for synthetic chemistry. A number mono- bidentate ligands also proven be effective accelerating directed weakly coordinating auxiliaries, which provides great opportunities reactivity selectivity (including enantioselectivity) functionalization reactions.

Language: Английский

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

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(17), P. 6603 - 6743

Published: Jan. 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.

Language: Английский

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Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(23), P. 13810 - 13889

Published: Nov. 1, 2017

Transition-metal-catalyzed cross-coupling reactions have been well-established as indispensable tools in modern organic synthesis. One of the major research goals area is expanding scope coupling partners. In past decade, diazo compounds (or their precursors N-tosylhydrazones) emerged nucleophilic partners C-C single bond or C═C double formations transition-metal-catalyzed reactions. This type reaction involves following general steps. First, organometallic species generated by various processes, including oxidative addition, transmetalation, cyclization, cleavage, and C-H activation. Subsequently, reacts with substrate to generate metal carbene intermediate, which undergoes rapid migratory insertion form a bond. The new from may undergo transformations. carbene-based has proven be general: transition metals Pd, Cu, Rh, Ni, Co, Ir are effective catalysts; also extended substrates other than compounds; cascade processes devised based on insertion. review will summarize achievements made this field since 2001.

Language: 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, Journal Year: 2020, Volume and Issue: 120(3), P. 1788 - 1887

Published: Jan. 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.

Language: Английский

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Organocatalysis in Inert C–H Bond Functionalization

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 9433 - 9520

Published: Feb. 13, 2017

As two coexisting and fast-growing research fields in modern synthetic chemistry, the merging of organocatalysis C–H bond functionalization is well foreseeable, joint force along this line has been demonstrated to be a powerful approach making inert more viable, predictable, selective. In review, we provide comprehensive summary over past decades. The review arranged by types bonds including alkane C–H, arene vinyl as those activated benzylic allylic alpha heteroatom such nitrogen oxygen. each section, discussion classified explicit organocatalytic mode involved.

Language: Английский

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Recent Advances in C–H Functionalization

The Journal of Organic Chemistry, Journal Year: 2016, Volume and Issue: 81(2), P. 343 - 350

Published: Jan. 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

Language: Английский

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Transition metal-catalyzed site- and regio-divergent C–H bond functionalization

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 46(14), P. 4299 - 4328

Published: Jan. 1, 2017

The regioselectivity of C–H functionalization reactions can be redirected to obtain regioisomeric products form the same starting materials.

Language: Английский

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Site-Selective C–H Functionalization by Decatungstate Anion Photocatalysis: Synergistic Control by Polar and Steric Effects Expands the Reaction Scope

ACS Catalysis, Journal Year: 2017, Volume and Issue: 8(1), P. 701 - 713

Published: Dec. 5, 2017

The synergistic control of the SH2 transition states hydrogen abstraction by polar and steric effects provides a promising strategy in achieving site-selective C(sp3)–H functionalization under decatungstate anion photocatalysis. By using this photocatalytic approach, C–H bonds alkanes, alcohols, ethers, ketones, amides, esters, nitriles, pyridylalkanes were functionalized site-selectively. In remarkable case 2,4-disubstituted cyclohexanone bearing five methyl, methylene, three methine bonds, one bond isoamyl tether was selectively functionalized.

Language: Английский

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