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 C–H bond functionalizations by the use of diverse directing groups

Organic Chemistry Frontiers, Journal Year: 2015, Volume and Issue: 2(9), P. 1107 - 1295

Published: Jan. 1, 2015

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

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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Recent applications of C–H functionalization in complex natural product synthesis

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(23), P. 8925 - 8967

Published: Jan. 1, 2018

In this review, recent examples featuring C-H functionalization in the synthesis of complex natural products are discussed. A focus is given to way which can influence logical process retrosynthesis, and review organized by type method functionalization.

Language: Английский

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C–H Functionalization in the Synthesis of Amino Acids and Peptides

Chemical Reviews, Journal Year: 2014, Volume and Issue: 114(18), P. 8775 - 8806

Published: Aug. 21, 2014

ADVERTISEMENT RETURN TO ISSUEReviewNEXTC–H Functionalization in the Synthesis of Amino Acids and PeptidesAnaïs F. M. Noisier Margaret A. Brimble*View Author Information School Chemical Sciences Maurice Wilkins Centre for Molecular Biodiscovery, The University Auckland, 23 Symonds Street, Auckland Central 1010, New Zealand*E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 18, 8775–8806Publication Date (Web):August 21, 2014Publication History Received9 April 2014Published online21 August inissue 24 September 2014https://doi.org/10.1021/cr500200xCopyright © 2014 American SocietyRIGHTS & PERMISSIONSACS AuthorChoiceArticle Views18448Altmetric-Citations444LEARN ABOUT THESE METRICSArticle Views are COUNTER-compliant sum full text article downloads since November 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 InReddit (8 MB) Get e-AlertsSUBJECTS:Anions,Arylation,Functionalization,Monomers,Peptides proteins e-Alerts

Language: Английский

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Syntheses and Transformations of α-Amino Acids via Palladium-Catalyzed Auxiliary-Directed sp³ C–H Functionalization

Accounts of Chemical Research, Journal Year: 2016, Volume and Issue: 49(4), P. 635 - 645

Published: March 25, 2016

Conspectusα-Amino acids (αAA) are one of the most useful chiral building blocks for synthesis. There numerous general strategies that have commonly been used αAA synthesis, many which employ de novo synthesis focused on enantioselective bond construction around Cα center and others consider conversion existing precursors carrying suitable functional groups side chains (e.g., serine aspartic acid). Despite significant advances in synthetic methodology, efficient enantiopure αAAs complex chains, as seen peptide natural products, remains challenging. Complementary to these "conventional" strategies, a strategy based selective functionalization chain C–H bonds, particularly sp3 hybridized various readily available may provide more straightforward broadly applicable means transformation αAAs. However, hurdles related low reactivity C(sp3)–H bonds difficulty controlling selectivity must be overcome realize potential chemistry this application. Over past few years, we carried out systematic investigation palladium-catalyzed bidentate auxiliary-directed reactions substrates. Our utilize two different types amide-linked auxiliary groups, attached at N or C terminus substrates, exert complementary regio- stereocontrol through palladacycle intermediates. A variety can undergo multiple modes functionalization, including arylation, alkenylation, alkynylation, alkylation, alkoxylation, intramolecular aminations, β, γ, even δ positions form new products with diverse structures. In addition transforming previously unreachable positions, enable retrosynthetic logic basic from common alanine precursor. This approach reduces by bypassing requirement relies convergent single-bond coupling transformations β-methyl position access wide range β-monosubstituted Moreover, further β-methylene generate β-branched stereoselective programmable fashion. These offer methods challenging facilitate total products.

Language: Английский

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Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp³)–H Bonds

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(24), P. 14957 - 15074

Published: Oct. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Language: Английский

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Iridium-Catalyzed Intermolecular Amidation of sp³ C–H Bonds: Late-Stage Functionalization of an Unactivated Methyl Group

Journal of the American Chemical Society, Journal Year: 2014, Volume and Issue: 136(11), P. 4141 - 4144

Published: Feb. 28, 2014

Reported herein is the iridium-catalyzed direct amidation of unactivated sp3 C–H bonds. With sulfonyl and acyl azides as amino source, occurs efficiently under mild conditions over a wide range methyl groups with high functional group tolerance. This procedure can be successfully applied for introduction an into complex compounds thus serve powerful synthetic tool late-stage functionalization.

Language: Английский

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