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

Chemical Society Reviews, Год журнала: 2016, Номер 45(23), С. 6462 - 6477

Опубликована: Янв. 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.

Язык: Английский

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Recent advances in transition-metal-catalyzed reactions of alkynes with isoxazoles

Organic & Biomolecular Chemistry, Год журнала: 2017, Номер 15(40), С. 8483 - 8492

Опубликована: Янв. 1, 2017

In this review, recent progress in the transition-metal-catalyzed formal annulations of alkynes with isoxazoles for efficient synthesis N-heterocycles is discussed.

Язык: Английский

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Cooperative Co(III)/Cu(II)-Catalyzed C–N/N–N Coupling of Imidates with Anthranils: Access to 1H-Indazoles via C–H Activation

Organic Letters, Год журнала: 2016, Номер 18(15), С. 3662 - 3665

Опубликована: Июль 14, 2016

Cooperative cobalt- and copper-catalyzed C–H activation of imidate esters oxidative coupling with anthranils allowed efficient synthesis 1H-indazoles in the absence metal oxidants. The anthranil acts as a convenient aminating reagent well an organic oxidant this transformation. copper catalyst likely functions at stage N–N formation.

Язык: Английский

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Cobalt(III)- and Rhodium(III)-Catalyzed C–H Amidation and Synthesis of 4-Quinolones: C–H Activation Assisted by Weakly Coordinating and Functionalizable Enaminone

Organic Letters, Год журнала: 2017, Номер 19(7), С. 1812 - 1815

Опубликована: Март 30, 2017

Cobalt(III) and rhodium(III) catalysts exhibited complementary scope in C–H amidation of aryl enaminones. The reactions proceeded with broad under the assistance a weakly coordinating bifunctional enaminone directing group. electrophilicity group can be further utilized subsequent hydrolysis–cyclization to afford NH 4-quinolones telescoping reactions.

Язык: Английский

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Catalyst‐Controlled Regiodivergent Alkyne Insertion in the Context of C−H Activation and Diels–Alder Reactions: Synthesis of Fused and Bridged Cycles

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(28), С. 8163 - 8167

Опубликована: Май 17, 2017

Abstract Rhodium(III)‐ and cobalt(III)‐catalyzed C−H activation of indoles coupling with 1,6‐enynes is discussed. Under rhodium(III) catalysis, the alkyne insertion follows 2,1‐regioselectivity a subsequent type‐I intramolecular Diels–Alder reaction (IMDA) to afford [6,5]‐fused cycles. When catalyzed by cobalt(III) congener, 1,2‐insertion preferred, followed rare type‐II IMDA, thus leading bridged [3,3,1]‐cycles. This selectivity was mainly tuned steric sensitivity catalyst.

Язык: Английский

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Chelation-Assisted Rhodium-Catalyzed Direct Amidation with Amidobenziodoxolones: C(sp²)–H, C(sp³)–H, and Late-Stage Functionalizations

ACS Catalysis, Год журнала: 2016, Номер 6(9), С. 5930 - 5934

Опубликована: Авг. 3, 2016

Air-stable and convenient amidobenziodoxolones as an amidating reagent were disclosed to enable direct amidation on a wide range of C(sp2)–H bonds (hetero)arenes alkenes, well unactivated C(sp3)–H under RhIII catalysis. The approach access 49 examples structurally diverse amides is featured by mild conditions, complete chemoselectivity regioselectivity, broad substrate scope (not limited strongly heterocyclic coordinating groups), tolerance valuable functional substituents, such unprotected amine hydroxyl groups. synthetic applicability this protocol also demonstrated late-stage functionalization biologically important scaffolds.

Язык: Английский

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Pd‐Catalyzed Dearomatization of Anthranils with Vinylcyclopropanes by [4+3] Cyclization Reaction

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(17), С. 5739 - 5743

Опубликована: Фев. 27, 2019

Abstract Dearomatization of anthranils with vinylcyclopropanes (VCPs) by Pd‐catalyzed [4+3] cyclization reaction has been realized. In the presence a catalytic amount borane as an activator, bridged cyclic products were obtained in good to excellent yields stereoselectivities. By introducing chiral PHOX ligand ( L5 ), asymmetric dearomatization reactions proceeded enantioselectivity. Borane plays key role for reactivity, likely owing formation borane–anthranil complex which confirmed NMR experiments.

Язык: Английский

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Rhodium(III)-Catalyzed C6-Selective Arylation of 2-Pyridones and Related Heterocycles Using Quinone Diazides: Syntheses of Heteroarylated Phenols

The Journal of Organic Chemistry, Год журнала: 2017, Номер 82(7), С. 3612 - 3621

Опубликована: Март 9, 2017

An efficient, direct C6-arylation of 2-pyridones has been successfully accomplished with quinone diazides under Rh(III)-catalyzed redox-neutral conditions. The optimized method is simple, mild, and highly regioselective a broad substrate scope. strict regioselectivity guided by the pyridyl substituent attached to nitrogen pyridone ring. As directing 2-pyridyl group can easily be removed at any suitable stage after functionalization, provides facile access complex heteroarylated phenol moieties wide-ranging heterocyclic scaffolds.

Язык: Английский

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