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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Transition‐Metal‐Mediated and ‐Catalyzed C−F Bond Activation by Fluorine Elimination

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(2), С. 390 - 402

Опубликована: Июнь 28, 2018

Abstract The activation of carbon–fluorine (C−F) bonds is an important topic in synthetic organic chemistry. Metal‐mediated and ‐catalyzed elimination β‐ or α‐fluorine proceeds under milder conditions than oxidative addition to C−F bonds. initiated from organometallic intermediates having fluorine substituents on carbon atoms β α metal centers, respectively. Transformations through these processes (C−F bond cleavage), which are typically preceded by carbon–carbon (or carbon–heteroatom) formation, have been increasingly developed the past five years as methods. In this Minireview, we summarize applications transition‐metal‐mediated chemistry a historical perspective with early studies systematic recent studies.

Язык: Английский

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Nickel-Catalyzed Defluorinative Reductive Cross-Coupling of gem-Difluoroalkenes with Unactivated Secondary and Tertiary Alkyl Halides

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(36), С. 12632 - 12637

Опубликована: Авг. 29, 2017

Herein, we described a nickel-catalyzed monofluoroalkenylation through defluorinative reductive cross-coupling of gem-difluoroalkenes with alkyl halides. Key to the success this strategy is combination C–F cleavage halides activation. This reaction enables convenient synthesis large variety functionalized monofluoroalkenes under mild conditions broad functional group compatibility and excellent Z-selectivity. The Ni catalysis (Bpin)2/K3PO4 as terminal reductant promoted efficient C(sp2)–C(sp3) formation especially generation all-carbon quaternary centers high chemoselectivity.

Язык: Английский

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Rhodium(iii)-catalyzed chemodivergent annulations between N-methoxybenzamides and sulfoxonium ylides via C–H activation

Chemical Communications, Год журнала: 2018, Номер 54(6), С. 670 - 673

Опубликована: Янв. 1, 2018

Rhodium-catalyzed and acid-controlled chemodivergent annulations between N-methoxybenzamides sulfoxonium ylides have been realized.

Язык: Английский

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C–F/C–H Functionalization by Manganese(I) Catalysis: Expedient (Per)Fluoro-Allylations and Alkenylations

ACS Catalysis, Год журнала: 2017, Номер 7(6), С. 4209 - 4213

Опубликована: Май 11, 2017

C–F/C–H functionalizations proved to be viable within a versatile manganese(I) catalysis manifold. Thus, wealth of fluorinated alkenes were employed in through facile C–H activation. The robust nature the regime was among others reflected by first activation with perfluoroalkenes as well racemization-free on imines, amino acids, and peptides.

Язык: Английский

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Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Chemical Reviews, Год журнала: 2022, Номер 122(24), С. 17479 - 17646

Опубликована: Окт. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Язык: Английский

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Metal-catalysed C–Het (F, O, S, N) and C–C bond arylation

Chemical Society Reviews, Год журнала: 2021, Номер 50(16), С. 8903 - 8953

Опубликована: Янв. 1, 2021

The formation of C–aryl bonds has been the focus intensive research over last decades for construction complex molecules from simple, readily available feedstocks.

Язык: Английский

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China's flourishing synthetic organofluorine chemistry: innovations in the new millennium

National Science Review, Год журнала: 2017, Номер 4(3), С. 303 - 325

Опубликована: Май 1, 2017

Abstract The new millennium has witnessed the rapid development of synthetic organofluorine chemistry all over world, and chemists in China have made significant contributions this field. This review aims to provide a brief introduction China's primary innovations from 2000 early 2017, covering fluorination, fluoroalkylation, fluoromethylthiolation, fluoroolefination polyfluoroarylation, as well synthesis with fluorinated building blocks. Recent advances difluorocarbene carbon–fluorine bond activation are also discussed. As conclusion, ends some personal perspectives on future chemistry.

Язык: Английский

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Stereoselective Synthesis of Z Fluoroalkenes through Copper‐Catalyzed Hydrodefluorination of gem‐Difluoroalkenes with Water

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(43), С. 13342 - 13346

Опубликована: Авг. 31, 2017

A copper catalytic system was established for the stereoselective hydrodefluorination of gem-difluoroalkenes through C-F activation to synthesize various Z fluoroalkenes. H2 O is used as hydrogen source fluorine acceptor moiety. This mild shows good-functional group compatibility, accepting a range carbonyls precursors gem-difluoroalkenes, including aliphatic, aromatic, and α,β-unsaturated aldehydes even ketones. It serves powerful synthetic method late-stage modification complex compounds.

Язык: Английский

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