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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The medicinal chemist's toolbox for late stage functionalization of drug-like molecules

Chemical Society Reviews, Journal Year: 2015, Volume and Issue: 45(3), P. 546 - 576

Published: Oct. 28, 2015

The advent of modern C-H functionalization chemistries has enabled medicinal chemists to consider a synthetic strategy, late stage (LSF), which utilizes the bonds drug leads as points diversification for generating new analogs. LSF approaches offer promise rapid exploration structure activity relationships (SAR), generation oxidized metabolites, blocking metabolic hot spots and preparation biological probes. This review details toolbox intermolecular with proven applicability drug-like molecules, classified by regioselectivity patterns, gives guidance on how systematically develop strategies using these patterns other considerations. In addition, number examples illustrate have been used impact actual discovery chemical biology efforts.

Language: Английский

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Transition-Metal-Catalyzed C–N Bond Forming Reactions Using Organic Azides as the Nitrogen Source: A Journey for the Mild and Versatile C–H Amination

Accounts of Chemical Research, Journal Year: 2015, Volume and Issue: 48(4), P. 1040 - 1052

Published: March 30, 2015

Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for development efficient selective methodologies allowing facile construction carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions been established as one most general protocols bond formation, these methods require starting materials equipped with groups such (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts halide salts byproducts. To address this aspect, a transition-metal-catalyzed direct C-H amination approach has emerged step- atom-economical alternative conventional reactions. However, despite significant recent advances metal-mediated reactions, available procedures need harsh conditions requiring external oxidants. In context, we were curious see whether mild protocol could be achieved using organic azides amino source. We envisaged that dual role an environmentally benign source also internal oxidant via N-N2 cleavage would key develop employing azides. An additional advantage was anticipated: sole byproduct is molecular nitrogen (N2) under perspective catalytic conditions. This Account mainly describes our research efforts on rhodium- iridium-catalyzed Under initially optimized Rh(III)-catalyzed conditions, not only sulfonyl but aryl- alkyl utilized sources reaction various types C(sp(2))-H bonds bearing directing pyridine, amide, ketoxime. More recently, new catalyst system Ir(III) species developed amidation arenes alkenes acyl exceptionally As extension, primary C(sp(3))-H realized basis superior activity Cp*Ir(III) catalyst. Mechanistic investigations revealed cycle operated three stages: (i) chelation-assisted metallacycle formation cleavage; (ii) through situ generation metal-nitrenoid intermediate followed by insertion imido moiety metal carbon bond; (iii) product release protodemetalation concomitant regeneration. addition, summarizes ruthenium- cobalt-catalyzed azides, own other groups. Comparative studies relative performance those systems are briefly described.

Language: Английский

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New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(5), P. 2613 - 2692

Published: Feb. 17, 2020

Transition-metal catalyzed reactions that are able to construct complex aliphatic amines from simple, readily available feedstocks have become a cornerstone of modern synthetic organic chemistry. In light the ever-increasing importance across range chemical sciences, this review aims provide concise overview transition-metal approaches alkylamine synthesis and their functionalization. Selected examples amine bond forming include: (a) hydroamination hydroaminoalkylation, (b) C(sp3)–H functionalization, (c) visible-light-mediated photoredox catalysis.

Language: Английский

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Functionalization of C(sp ³ )–H bonds using a transient directing group

Science, Journal Year: 2016, Volume and Issue: 351(6270), P. 252 - 256

Published: Jan. 14, 2016

Amino acids can lend palladium a hand Metals such as rhodium and (Pd) are adept at activating otherwise inert carbon-hydrogen bonds toward useful reactivity. To get properly oriented, they often require some help from oxygen or nitrogen groups nearby. Appending removing these directing groups, however, detracts the efficiency of chemical synthesis. Zhang et al. show that amino act temporary in Pd-catalyzed coupling arenes with aldehydes ketones. By reversibly binding to latter substrates just long enough for Pd catalysis ensue, eliminate need more laborious group manipulations. Science , this issue p. 252

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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Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 57(1), P. 62 - 101

Published: Dec. 5, 2017

Abstract The functionalization of C(sp 3 )−H bonds streamlines chemical synthesis by allowing the use simple molecules and providing novel synthetic disconnections. Intensive recent efforts in development new reactions based on C−H have led to its wider adoption across a range research areas. This Review discusses strengths weaknesses three main approaches: transition‐metal‐catalyzed activation, 1, n ‐hydrogen atom transfer, carbene/nitrene for directed unactivated bonds. For each strategy, scope, reactivity different bonds, position reacting relative directing group, stereochemical outcomes are illustrated with examples literature. aim this is provide guidance inspire future area.

Language: Английский

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C–H activation

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

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Mechanistic Studies on the Rh(III)-Mediated Amido Transfer Process Leading to Robust C–H Amination with a New Type of Amidating Reagent

Journal of the American Chemical Society, Journal Year: 2015, Volume and Issue: 137(13), P. 4534 - 4542

Published: March 20, 2015

Mechanistic investigations on the Cp*Rh(III)-catalyzed direct C-H amination reaction led us to reveal new utility of 1,4,2-dioxazol-5-one and its derivatives as highly efficient amino sources. Stepwise analysis C-N bond-forming process showed that competitive binding rhodium metal center amidating reagent or substrate is closely related efficiency. In this line, 1,4,2-dioxazol-5-ones were observed have a strong affinity cationic Rh(III) giving rise dramatically improved amidation efficiency when compared azides. Kinetics computational studies suggested high reactivity can also be attributed low activation energy an imido-insertion in addition coordination ability. While characterization Cp*Rh(III) complex bearing was achieved, facile conversion amido-inserted rhodacycle allowed for clear picture process. The newly developed applicable broad range substrates with functional group tolerance, releasing carbon dioxide single byproduct. Additional attractive features source, such they are more convenient prepare, store, use corresponding azides, take step closer toward ideal protocol.

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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