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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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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Enantioselective Cobalt(III)‐Catalyzed C−H Activation Enabled by Chiral Carboxylic Acid Cooperation

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(47), С. 15425 - 15429

Опубликована: Окт. 6, 2018

The enantioselective cobalt(III)-catalyzed C-H alkylation was achieved through the design of a novel chiral acid. activation characterized by high position-, regio- and enantio-control under exceedingly mild reaction conditions. Thereby, robust cooperative cobalt(III) catalysis proved tolerant valuable electrophilic functional groups, including hydroxyl, bromo, iodo substituents. Mechanistic studies revealed considerable additive effect on kinetics negative non-linear-effect.

Язык: Английский

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Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3452 - 3506

Опубликована: Март 3, 2022

Transition-metal-catalyzed C–H bond functionalizations have had an enormous influence on organic synthesis in recent times. However, the use of low-abundance 4d and 5d metals is almost inevitable, they are high demand. This will be a cause concern, hence, it important to develop methods based 3d metals, which widely present Earth's crust. In this regard, metal catalysts or their precursors for catalysis, general, functionalizations, particular, has gained significant momentum The major development catalytic with been achieved predominantly strongly coordinating directing groups such as pyridyl, pyrimidinyl, pyrazolyl, 8-amino-quinolinyl groups. Thus, prefunctionalization substrates these necessary, contradicts step- atom-economy activation. commonly available functional aldehyde, ketone, carboxylic acid, amide, hydroxy, N-oxides loosely bind through weak-coordination. These weakly orient activate regioselectively without need preinstalled Although challenging, contemporary topic actively pursued by many researchers Through article, we provide comprehensive overview metal-catalyzed, coordinating, directing-group-enabled reported until March 2021.

Язык: Английский

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Directing group migration strategy in transition-metal-catalysed direct C–H functionalization

Chemical Society Reviews, Год журнала: 2021, Номер 50(6), С. 3677 - 3689

Опубликована: Янв. 1, 2021

In this tutorial review, the rapid advances of directing group (DG) migration in transition-metal-catalysed direct C–H activation was presented through analyzing and comparing different bond cleavage trigger DG (including N–O, N–C, N–N or O–C).

Язык: Английский

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Recent advances using [Cp*Co(CO)I₂] catalysts as a powerful tool for C–H functionalisation

Dalton Transactions, Год журнала: 2017, Номер 46(30), С. 9721 - 9739

Опубликована: Янв. 1, 2017

This perspective highlights recent applications of Cp*Co^III catalysts in C–H functionalisation protocols, exemplifying both terminal couplings and heterocycle formation.

Язык: Английский

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Recent advances in cobalt-catalysed C–H functionalizations

Organic & Biomolecular Chemistry, Год журнала: 2019, Номер 17(48), С. 10119 - 10141

Опубликована: Янв. 1, 2019

Ready availability, low cost and toxicity of cobalt salts have redirected the attention researchers away from noble metals, such as Pd, Rh, Ir, towards Co in field C-H functionalization. In this context, examples Co-catalysed functionalization exponentially grown over last few decades. This present review focuses on most recent developments C(sp2)-H C(sp3)-H functionalizations. Included is also a comprehensive overview enantioselective transformations.

Язык: Английский

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Late‐Stage Peptide Diversification through Cobalt‐Catalyzed C−H Activation: Sequential Multicatalysis for Stapled Peptides

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(6), С. 1684 - 1688

Опубликована: Ноя. 30, 2018

Bioorthogonal late-stage diversification of structurally complex peptides has enormous potential for drug discovery and molecular imaging. In recent years, transition-metal-catalyzed C-H activation emerged as an increasingly viable tool peptide modification. Despite major accomplishments, these strategies largely rely on expensive palladium catalysts. We herein report unprecedented cobalt(III)-catalyzed activation, which enables the direct functionalization peptides, sets stage a multicatalytic activation/alkene metathesis/hydrogenation strategy assembly novel cyclic peptides.

Язык: Английский

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Regioselective Direct C‐Alkenylation of Indoles

Chemistry - A European Journal, Год журнала: 2017, Номер 23(64), С. 16115 - 16151

Опубликована: Июнь 22, 2017

Abstract The direct introduction of alkenyl groups into the indole framework avoiding its preliminary functionalization can be carried out using different synthetic strategies. Transition‐metal complexes facilitate C−H activation indoles or alkenes allowing an efficient Csp 2 ‐ bond formation. hydroindolation alkynes catalyzed by same metal various acidic promoters also pursued for alkenylation process. Conjugate addition electron‐poor and condensation carbonyl derivatives with are interest this purpose. regiochemical control exploited intrinsic C‐3 reactivity ring. a suitable directing group at nitrogen atom allows preparation C‐2 alkenylated transition reactions. This review collects fundamental contributions in field reported literature during last fifteen years.

Язык: Английский

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Cp*Co^III-Catalyzed Branch-Selective Hydroarylation of Alkynes via C–H Activation: Efficient Access to α-gem-Vinylindoles

ACS Catalysis, Год журнала: 2017, Номер 7(10), С. 7296 - 7304

Опубликована: Сен. 12, 2017

An efficient, atom-economical, and regioselective insertion of indoles into terminal alkynes has been realized via cobalt(III)-catalyzed C–H activation under mild conditions, leading to efficient synthesis α-gem-vinylindoles. The the follows a rare 1,2-selectivity, silyl alkynes, alkyl propargyl alcohols, protected amines are all applicable. mechanism this hydroarylation system studied in detail by combination experimental computational approaches. In reaction regioselectivity is dictated steric effects alkyne substituent, especially protonolysis stage. However, for amines, selectivity results from electronic during step, with being insignificant determination selectivity. internal also coupled high efficiency but low regioselectivity. Comparisons cobalt, rhodium, iridium catalysts have made terms reactivity, both cobalt catalysts.

Язык: Английский

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