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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Mild metal-catalyzed C–H activation: examples and concepts

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(10), P. 2900 - 2936

Published: Jan. 1, 2016

C–H Activation reactions that proceed under mild conditions are more attractive for applications in complex molecule synthesis. Mild transformations reported since 2011 reviewed and the different concepts strategies have enabled their mildness discussed.

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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Late-stage C–H functionalization offers new opportunities in drug discovery

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(8), P. 522 - 545

Published: July 13, 2021

Language: Английский

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Catalytic Methods for Aromatic C–H Amination: An Ideal Strategy for Nitrogen-Based Functional Molecules

ACS Catalysis, Journal Year: 2015, Volume and Issue: 6(2), P. 610 - 633

Published: Dec. 7, 2015

Transformations of aromatic compounds into the corresponding amines, amides, and imides through carbon–hydrogen (C–H) bond functionalization represent one most step- atom-economical methods for synthesis arylamine compounds. Because arylamines are privileged structures in materials- biology-oriented functional molecules, development novel efficient synthetic C–H amination has received significant attention from a wide range research fields including materials pharmaceuticals. This review covers recent advances catalytic reactions. An array recently developed new reactions categorized by nature substrates: (1) 5-membered heteroarenes, (2) arenes having nitrogen moiety molecule (intramolecular amination), (3) directing group, (4) simple with excess amounts, (5) as limiting reagents.

Language: Английский

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Comparative Catalytic Activity of Group 9 [Cp*M^III] Complexes: Cobalt‐Catalyzed CH Amidation of Arenes with Dioxazolones as Amidating Reagents

Angewandte Chemie International Edition, Journal Year: 2015, Volume and Issue: 54(47), P. 14103 - 14107

Published: Sept. 25, 2015

A procedure for the [Cp*Co(III)]-catalyzed direct C-H amidation of arenes with dioxazolone has been developed. This reaction proceeds under straightforward and mild conditions a broad range substrates, including anilides. comparative study on catalytic activity Group 9 [{Cp*MCl2}2] complexes revealed unique efficiency cobalt catalyst.

Language: Английский

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Transition metal-catalysed couplings between arenes and strained or reactive rings: combination of C–H activation and ring scission

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(23), P. 6462 - 6477

Published: Jan. 1, 2016

Transition metal-catalysed systems of C–H activation arenes in combination with opening strained or reactive three, four, and five membered rings are summarized this review.

Language: Английский

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Selective formation of γ-lactams via C–H amidation enabled by tailored iridium catalysts

Science, Journal Year: 2018, Volume and Issue: 359(6379), P. 1016 - 1021

Published: March 1, 2018

Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form γ-lactam rings has traditionally been hindered by competing isocyanate formation. We report the application theory and mechanism studies optimize a class pentamethylcyclopentadienyl iridium(III) catalysts for suppression this pathway. Modulation stereoelectronic properties auxiliary bidentate ligands be more electron-donating was suggested density functional calculations lower C-H barrier favoring desired reaction. These transform wide range 1,4,2-dioxazol-5-ones, carbonylnitrene precursors easily accessible from carboxylic acids, corresponding γ-lactams via sp3 sp2 amidation with exceptional selectivity. The power method further demonstrated successful late-stage functionalization amino acid derivatives other bioactive molecules.

Language: Английский

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Catalytic Transformations of Functionalized Cyclic Organic Carbonates

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(42), P. 13735 - 13747

Published: June 6, 2018

Functionalized cyclic organic carbonates and related heterocycles have emerged as highly versatile heterocyclic substrates for ring-opening decarboxylative catalytic transformations allowing the development of new stereo- enantioselective C-N, C-O, C-C, C-S C-B bond formation reactions. Transition-metal-mediated conversions only recently been rejuvenated powerful approaches towards preparation more complex molecules. This minireview will highlight potential structurally with a focus on their synthetic value mechanistic manifolds that are involved upon conversion.

Language: Английский

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Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C–H Functionalization

Accounts of Chemical Research, Journal Year: 2017, Volume and Issue: 51(1), P. 170 - 180

Published: Dec. 22, 2017

ConspectusThe history of transition metal catalysis is heavily steeped in ligand design, clearly demonstrating the importance this approach. The intimate relationship between and can profoundly affect outcome a reaction, often impacting selectivity, physical properties, lifetime catalyst. Importantly, metal–ligand provide near limitless opportunities for reaction discovery. Over past several years, transition-metal-catalyzed C–H bond functionalization reactions have been established as critical foundation organic chemistry that provides new forming strategies. Among d-block elements, palladium arguably one most popular metals to accomplish such transformations. One possible explanation achievement could be broad set phosphine amine based ligands available chemist's toolbox compatible with palladium. In parallel, other investigated functionalization. them, pentamethylcyclopentadienyl (Cp*) Rh(III) complexes emerged powerful mode transformations providing spectrum reactivity. This approach possesses advantage very low catalyst loading, are typically performed under mild conditions allowing functional group tolerance. Cp*Rh(III) considered privileged plethora involving cleavage event developed. search alternative cyclopentadienyl has eclipsed by tremendous effort devoted exploring considerable scope catalyzed complexes, despite potential strategy enabling Thus, modification efforts an exception research directed toward rhodium catalysts sparse. Recently, chiral appeared enantioselective Rh(III)-catalyzed performed. Alongside ligands, equally important collection achiral cyclopentadienyl-derived also emerged. design already translated significant success solving inherent problems reactivity selectivity encountered throughout development Account describes evolution skeletons Rh(III)-catalysis since introduction present. Specific emphasis placed on synthetic applications achieved mono-, di-, or pentasubstituted exhibiting stunning effect selectivity. Furthermore, underlying question when dealing strategies explain reason outperforms another. Conjecture speculation abound, but extensive characterization their steric electronic properties carried out information about all contribute our understanding give crucial pieces solve puzzle.

Language: Английский

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