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

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 9247 - 9301

Опубликована: Янв. 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.

Язык: Английский

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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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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, Год журнала: 2017, Номер 57(1), С. 62 - 101

Опубликована: Дек. 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.

Язык: Английский

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

Chemical Reviews, Год журнала: 2021, Номер 121(24), С. 14957 - 15074

Опубликована: Окт. 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.

Язык: Английский

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Komplementäre Strategien für die dirigierte C(sp³)‐H‐Funktionalisierung: ein Vergleich von übergangsmetallkatalysierter Aktivierung, Wasserstoffatomtransfer und Carben‐ oder Nitrentransfer

Angewandte Chemie, Год журнала: 2017, Номер 130(1), С. 64 - 105

Опубликована: Дек. 5, 2017

Abstract Funktionalisierungen von C(sp 3 )‐H‐Bindungen verkürzen und vereinfachen chemische Synthesen, indem sie die Verwendung einfacher Moleküle ermöglichen neuartige Retrosynthesen bereitstellen. Intensive Forschungen, auf Entwicklung neuer Reaktionen basierend dem Ansatz der C‐H‐Funktionalisierung abzielten, haben zur weiten Verbreitung dieser Methoden in einer Vielzahl Bereichen geführt. Dieser Aufsatz erörtert Stärken Schwächen drei Hauptstrategien – übergangsmetallkatalysierte C‐H‐Aktivierung, 1, n ‐Wasserstoffatomtransfer übergangsmetallkatalysierter Carben‐ oder Nitrentransfer gezielten Funktionalisierung nichtaktivierter )‐H‐Bindungen. Für jede Strategie werden Anwendungsbereich, Reaktivität verschiedener C‐H‐Bindungen, Position reagierenden C‐H‐Bindungen bezüglich dirigierenden Gruppe stereochemischen Auswirkungen mit Beispielen aus Literatur veranschaulicht. Das Ziel dieses Aufsatzes ist es, Anwender C‐H‐Funktionalisierungsreaktionen eine Orientierungshilfe zu geben künftige Forschungen diesem Gebiet anzuregen.

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Plausible Rh(V) Intermediates in Catalytic C–H Activation Reactions

ACS Catalysis, Год журнала: 2017, Номер 8(1), С. 242 - 257

Опубликована: Ноя. 20, 2017

Catalysis by defined transition-metal complexes has captivated the attention of scientific community over last decades. The well-documented utility Rh(III) in C–H activation reactions have enabled development a plethora new catalytic methods. High-valent species were first predicted palladium-based transformations. From those early studies, it was apparent that differences reactivity and selectivity could be expected. By analogy, higher valent Rh(V) represent approach offer different opportunities to improve broaden current state-of-the-art field.

Язык: Английский

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Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(16), С. 2653 - 2675

Опубликована: Апрель 21, 2023

Abstract Hypervalent iodine compounds have found broad application in modern organic chemistry as reagents and catalysts. Cyclic hypervalent based on the benziodoxole heterocyclic system higher stability compared to their acyclic analogues, which makes possible preparation safe handling of with special ligands such azido, cyano, trifluoromethyl groups. Numerous iodine‐substituted derivatives been prepared utilized for transfer substituent substrate. Reactions these substrates can be performed under metal‐free conditions, presence transition metal catalysts, or using photocatalysts photoirradiation conditions. In this review, we focus most recent synthetic applications cyclic iodine(III) following ligands: N 3 , NHR, CN, CF SCF OR, OAc, ONO 2 C(=N )CO R. The review covers literature published mainly last 5 years.

Язык: Английский

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Rhodium(iii)-catalyzed regio- and stereoselective benzylic α-fluoroalkenylation with gem-difluorostyrenes

Chemical Communications, Год журнала: 2017, Номер 53(74), С. 10326 - 10329

Опубликована: Янв. 1, 2017

Rhodium(iii)-catalyzed mild benzylic α-fluoroalkenylation of 8-methylquinolines with gem-difluorostyrenes has been developed. This reaction occurred via C-H activation and C-F cleavage is applicable to a wide range substrates, leading the synthesis Z-alkenyl fluorides under redox-neutral conditions high regio- stereoselectivity.

Язык: Английский

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Rh(III)‐Catalyzed Selective C8−H Acylmethylation of Quinoline N‐Oxides

Advanced Synthesis & Catalysis, Год журнала: 2018, Номер 360(21), С. 4068 - 4072

Опубликована: Авг. 17, 2018

Abstract A highly efficient Rh‐catalyzed regioselective C8−H acylmethylation of quinoline N‐ oxides with sulfoxonium ylides using oxide as the directing group under air atmosphere has been developed. This transformation generality a broad scope substrates, avoids external oxidants, and provides an protocol to acylmethylated quinolines. magnified image

Язык: Английский

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Mechanism‐Driven Approach To Develop a Mild and Versatile C−H Amidation through Ir^III Catalysis

Chemistry - A European Journal, Год журнала: 2017, Номер 23(46), С. 11147 - 11152

Опубликована: Май 26, 2017

Abstract Described herein is a mechanism‐based approach to develop versatile C−H amidation protocol under Ir III catalysis. Reaction kinetics of key C−N coupling step with acyl azide and 1,4,2‐dioxazol‐5‐one led us conclude that dioxazolones are much more efficient in mediating the formation carbon−nitrogen bond from an iridacyclic intermediate. Computational analysis revealed origin higher reactivity asynchronous decarboxylation motion, which may facilitate Ir‐imido species. Importantly, stoichiometric was successfully translated into catalytic activity broad range substrates (18 different types), many regarded as challenging functionalize. Application new method enables late‐stage functionalization drug molecules.

Язык: Английский

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