3d Transition Metals for C–H Activation

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2192 - 2452

Опубликована: Ноя. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Язык: Английский

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

Nature Reviews Chemistry, Год журнала: 2021, Номер 5(8), С. 522 - 545

Опубликована: Июль 13, 2021

Язык: Английский

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(Pentamethylcyclopentadienyl)cobalt(III)‐Catalyzed C–H Bond Functionalization: From Discovery to Unique Reactivity and Selectivity

Advanced Synthesis & Catalysis, Год журнала: 2017, Номер 359(8), С. 1245 - 1262

Опубликована: Март 16, 2017

Abstract High‐valent (pentamethylcyclopentadienyl)cobalt(III) [Cp*Co(III)] catalysts were found as inexpensive alternatives to (pentamethylcyclopentadienyl)rhodium(III) [Cp*Rh(III)] in the field of C—H bond functionalization, and applied a variety transformations. In this review, after discovery early examples Cp*Co(III)‐catalyzed functionalization are summarized, unique reactivity selectivity Cp*Co(III) differences between cobalt rhodium catalysis intensively discussed. Such assumed be caused by lower electronegativity, hard nature, smaller ionic radius cobalt. magnified image

Язык: Английский

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Catalytic Transformations of Functionalized Cyclic Organic Carbonates

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(42), С. 13735 - 13747

Опубликована: Июнь 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.

Язык: Английский

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C–H functionalization by high-valent Cp*Co(iii) catalysis

Chemical Communications, Год журнала: 2017, Номер 53(22), С. 3165 - 3180

Опубликована: Янв. 1, 2017

Significant progress has been accomplished in directed C–H functionalization through the use of earth-abundant and inexpensive first-row transition metals.

Язык: Английский

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Direct Functionalization of C−H Bonds by Iron, Nickel, and Cobalt Catalysis

Chemistry - A European Journal, Год журнала: 2017, Номер 23(39), С. 9206 - 9232

Опубликована: Июнь 7, 2017

Abstract Non‐precious‐metal‐catalyzed reactions are of increasing importance in chemistry due to the outstanding ecological and economic properties these metals. In subfield metal‐catalyzed direct C−H functionalization reactions, recent years have shown an number publications dedicated this topic. Nickel, cobalt, last but not least iron, started enter a field which was long dominated by precious metals such as palladium, rhodium, ruthenium, iridium. The present review article summarizes development iron‐, nickel‐, cobalt‐catalyzed until end 2016, discusses scope limitations transformations.

Язык: Английский

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Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)‐Catalyzed Intermolecular Carboamination of Alkenes

Angewandte Chemie International Edition, Год журнала: 2016, Номер 55(48), С. 15166 - 15170

Опубликована: Окт. 27, 2016

Abstract Herein, we report an unprecedented regioselective and entirely atom‐economic cobalt(III)‐catalyzed method for the non‐annulative, intermolecular carboamination of alkenes. The methodology enables direct synthesis unnatural amino acid derivatives proceeds under redox‐neutral conditions with a completely C−C bond C−N formation. Furthermore, this reaction exemplifies inherently different mechanistic behavior Cp*Co III catalyst its Cp*Rh counterpart, especially towards β‐H‐elimination.

Язык: Английский

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Cobalt‐Catalyzed Annulation Reactions via C−H Bond Activation

ChemCatChem, Год журнала: 2017, Номер 10(4), С. 683 - 705

Опубликована: Ноя. 1, 2017

Abstract Considerable research attention has been directed towards the use of first‐row transition metals in organic synthesis. The more abundant, and less expensive cobalt is considered to be an effective alternative for second third‐row noble metals, especially C−H bond functionalization reactions. In this Minireview, we will summarize features, recent achievements Co‐catalyzed directing group assisted activation/cyclization reactions their mechanistic insights.

Язык: Английский

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