Mild metal-catalyzed C–H activation: examples and concepts

Chemical Society Reviews, Год журнала: 2016, Номер 45(10), С. 2900 - 2936

Опубликована: Янв. 1, 2016

C–H Activation reactions that proceed under mild conditions are more attractive for applications in complex molecule synthesis. Mild transformations reported since 2011 reviewed and the different concepts strategies have enabled their mildness discussed.

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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Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Chemical Reviews, Год журнала: 2020, Номер 120(3), С. 1788 - 1887

Опубликована: Янв. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

Язык: Английский

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Recent advances in copper-mediated chelation-assisted functionalization of unactivated C–H bonds

Organic Chemistry Frontiers, Год журнала: 2016, Номер 3(8), С. 1028 - 1047

Опубликована: Янв. 1, 2016

Recent advances in copper-mediated (both stoichiometric and catalytic) chelation-assisted functionalization of unactivated C–H bonds are reviewed.

Язык: Английский

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Strategic evolution in transition metal-catalyzed directed C–H bond activation and future directions

Coordination Chemistry Reviews, Год журнала: 2020, Номер 431, С. 213683 - 213683

Опубликована: Дек. 9, 2020

Язык: Английский

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A remarkable solvent effect of fluorinated alcohols on transition metal catalysed C–H functionalizations

Organic Chemistry Frontiers, Год журнала: 2016, Номер 3(3), С. 394 - 400

Опубликована: Янв. 1, 2016

Fluorinated solvents like 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and trifluoroethanol (TFE) have recently emerged as a remarkable synthetic hint allowing challenging C–H activation reactions.

Язык: Английский

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Site‐Selective δ‐C(sp³)−H Alkylation of Amino Acids and Peptides with Maleimides via a Six‐Membered Palladacycle

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(20), С. 5858 - 5862

Опубликована: Март 26, 2018

The site-selective functionalization of unactivated C(sp3 )-H bonds remains one the greatest challenges in organic synthesis. Herein, we report on δ-C(sp3 alkylation amino acids and peptides with maleimides via a kinetically less favored six-membered palladacycle presence more accessible γ-C(sp3 bonds. Experimental studies revealed that C-H bond cleavage occurs reversibly preferentially at γ-methyl over δ-methyl while subsequent proceeds exclusively is generated by δ-C-H activation. selectivity can be explained Curtin-Hammett principle. exceptional compatibility this various oligopeptides renders procedure valuable for late-stage peptide modifications. Notably, process also first palladium(II)-catalyzed Michael-type reaction through

Язык: Английский

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Site-Selective Alkenylation of δ-C(sp³)–H Bonds with Alkynes via a Six-Membered Palladacycle

Journal of the American Chemical Society, Год журнала: 2016, Номер 138(34), С. 10750 - 10753

Опубликована: Авг. 16, 2016

Most chelation-assisted aliphatic C-H activation proceeds through a kinetically favored five-membered cyclometalated intermediate. Here, we report the first site-selective alkenylation of δ-C(sp(3))-H in presence more accessible γ-C(sp(3))-H bonds via less six-membered palladacycle. A wide range functional groups are tolerated, and unique protocol can be applied to synthesis chiral piperidines. Moreover, mechanistic insights have been conducted elucidate origin unusual site-selectivity.

Язык: Английский

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Catalytic, Regioselective Hydrocarbofunctionalization of Unactivated Alkenes with Diverse C–H Nucleophiles

Journal of the American Chemical Society, Год журнала: 2016, Номер 138(44), С. 14705 - 14712

Опубликована: Окт. 6, 2016

Reactions that forge carbon–carbon (C–C) bonds are the bedrock of organic synthesis, widely used across chemical sciences. We report a transformation enables C–C to be constructed from two classes commonly available starting materials, alkenes and carbon–hydrogen (C–H) bonds. The reaction employs palladium(II) catalyst utilizes removable directing group both control regioselectivity carbopalladation enable subsequent protodepalladation. A wide range C–H nucleophiles, including 1,3-dicarbonyls, aryl carbonyls, electron-rich aromatics, viable partners, allowing Michael-type reactivity expanded beyond α,β-unsaturated carbonyl compounds unactivated alkenes. Applications this in drug diversification natural product total synthesis described. Stoichiometric studies support each proposed steps catalytic cycle.

Язык: Английский

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Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C–H Functionalization Enabled by Chiral Carboxylic Acid

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(18), С. 6810 - 6816

Опубликована: Апрель 28, 2021

Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining cleavage step remains undeveloped. Here we describe a activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using novel class chiral binaphthyl monocarboxylic acids as ligands, which can be easily and modularly prepared from 1,1'-binaphthyl-2,2'-dicarboxylic acid. A broad range sulfur-stereogenic were in high yields excellent enantioselectivities (up to 99% yield ee) via desymmetrization, kinetic resolution, parallel resolution. Furthermore, the resolution products transformed sulfoxides key intermediates for kinase inhibitors.

Язык: Английский

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