A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(17), P. 6603 - 6743

Published: Jan. 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.

Language: 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, Journal Year: 2020, Volume and Issue: 120(3), P. 1788 - 1887

Published: Jan. 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.

Language: Английский

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Computational Studies of Carboxylate-Assisted C–H Activation and Functionalization at Group 8–10 Transition Metal Centers

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 8649 - 8709

Published: May 22, 2017

Computational studies on carboxylate-assisted C-H activation and functionalization at group 8-10 transition metal centers are reviewed. This Review is organized by will cover work published from late 2009 until mid-2016. A brief overview of computational prior to 2010 also provided, this outlines the understanding in terms "ambiphilic metal-ligand assistance" (AMLA) "concerted metalation deprotonation" (CMD) concepts. then surveyed nature bond being activated (C(sp2)-H or C(sp3)-H), process involved (intramolecular with a directing intermolecular), context (stoichiometric within variety catalytic processes). aims emphasize connection between computation experiment highlight contribution chemistry our based activation. Some opportunities where interplay may contribute further areas applied identified.

Language: Английский

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Cross-coupling of aromatic esters and amides

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 46(19), P. 5864 - 5888

Published: Jan. 1, 2017

This review highlights the progress in transition-metal-catalyzed decarbonylative and non-decarbonylative cross-coupling of aromatic esters amides.

Language: Английский

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Photochemical Generation of Nitrogen-Centered Amidyl, Hydrazonyl, and Imidyl Radicals: Methodology Developments and Catalytic Applications

ACS Catalysis, Journal Year: 2017, Volume and Issue: 7(8), P. 4999 - 5022

Published: June 19, 2017

During the past decade, visible light photocatalysis has become a powerful synthetic platform for promoting challenging bond constructions under mild reaction conditions. These photocatalytic systems rely on harnessing energy purposes through generation of reactive but controllable free radical species. Recent progress in area established it as an enabling catalytic strategy and selective nitrogen-centered radicals. The application activation amides, hydrazones, imides represents valuable approach facilitating formation Within span only couple years, significant been made expediting amidyl, hydrazonyl, imidyl radicals from variety precursors. This Perspective highlights recent advances light-mediated these A particular emphasis is placed unique ability accessing elusive manifolds construction diversely functionalized nitrogen-containing motifs nontraditional disconnections contemporary chemistry.

Language: Английский

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Recent advances in positional-selective alkenylations: removable guidance for twofold C–H activation

Organic Chemistry Frontiers, Journal Year: 2017, Volume and Issue: 4(7), P. 1435 - 1467

Published: Jan. 1, 2017

Recent advances in transition-metal catalyzed positional-selective alkenylations via twofold C–H activation directed by removable or traceless directing groups are reviewed.

Language: Английский

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Late‐Stage Peptide Diversification by Position‐Selective C−H Activation

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(45), P. 14700 - 14717

Published: July 3, 2018

The late-stage modification of structurally complex peptides bears great potential for drug discovery, crop protection, and the pharmaceutical industry, among others. Whereas traditional approaches largely rely on prefunctionalizations, C-H activation catalysis has in recent years emerged as an increasingly powerful tool post-translational peptide modifications a step-economic manner. Herein, we summarize progress organometallic until June 2018, including position- chemoselective palladium-, ruthenium-, manganese-catalyzed processes.

Language: Английский

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Catalytic activations of unstrained C–C bond involving organometallic intermediates

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(18), P. 7078 - 7115

Published: Jan. 1, 2018

The cleavage of C-C bonds has been a great challenge owing to their thermodynamic and kinetic stability. To date, the progress made in this area mainly relied on reaction small rings, which is driven by releasing ring strain. Encouragingly, more examples non-strained have reported. This review provides comprehensive overview transition-metal-catalyzed bond activation relatively stable unstrained molecules that involves formation organometallic intermediates. In first section we focus achieved through β-carbon elimination, second oxidative addition low-valent metal summarized detail.

Language: Английский

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Metal-Mediated and Metal-Catalyzed Reactions Under Mechanochemical Conditions

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(15), P. 8344 - 8394

Published: May 27, 2020

The extraordinary impact of metal-based complexes on synthetic methods is still recognized nowadays, and attempts are currently undertaken to further extend the use metal-assisted chemistry environmentally friendly processes within strongly invoked green paradigm. In recent years, mechanochemistry seems provide attractive responses with processing having origins lost in mists time. Focusing panorama organic synthesis, this Review highlights some recently developed mechanochemical reactions introduce reader into fascinating, quite unexplored world mechanochemistry.

Language: Английский

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Transition-Metal-Catalyzed C–H Bond Activation for the Formation of C–C Bonds in Complex Molecules

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(12), P. 7692 - 7760

Published: May 10, 2023

Site-predictable and chemoselective C–H bond functionalization reactions offer synthetically powerful strategies for the step-economic diversification of both feedstock fine chemicals. Many transition-metal-catalyzed methods have emerged selective activation bonds. However, challenges regio- chemoselectivity with application to highly complex molecules bearing significant functional group density diversity. As molecular complexity increases within structures risks catalyst intolerance limited applicability grow number groups potentially Lewis basic heteroatoms. Given abundance bonds already diversified such as pharmaceuticals, natural products, materials, design selection reaction conditions tolerant catalysts has proved critical successful direct functionalization. such, innovations formation carbon–carbon been discovered developed overcome these limitations. This review highlights progress made metal-catalyzed C–C forming including alkylation, methylation, arylation, olefination targets.

Language: Английский

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