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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Transition-metal-catalyzed site-selective C7-functionalization of indoles: advancement and future prospects

Chemical Communications, Journal Year: 2018, Volume and Issue: 55(5), P. 572 - 587

Published: Dec. 5, 2018

C7-Decorated indoles are important structural motifs present in a plethora of bioactive and pharmaceutical compounds. Early stage developments for C7 modifications were realized through directed metallation (DOM) subsequent quenching with suitable electrophiles or by halogenation Cu(ii) halides. Direct C-7 functionalization is comparatively difficult compared to at C-2 C-3 positions owing the inherent reactivity pyrrole-type ring. However, recently transition-metal-catalyzed auxiliary assisted site-selective has emerged as an elegant synthetic tool carbon-carbon carbon-heteroatom bond formation diversify indoles. This article covers advancement, application mechanistic underpinnings evolved transformations otherwise inert C7-H up October 2018.

Language: Английский

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Ruthenaelectro-catalyzed C–H acyloxylation for late-stage tyrosine and oligopeptide diversification

Chemical Science, Journal Year: 2022, Volume and Issue: 13(12), P. 3461 - 3467

Published: Jan. 1, 2022

Ruthenaelectro( ii / iv )-catalyzed intermolecular C–H acyloxylations of oligopeptides have been developed by the guidance key experimental, CV and computational insights.

Language: Английский

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Palladium-Catalyzed Direct and Specific C-7 Acylation of Indolines with 1,2-Diketones

Organic Letters, Journal Year: 2021, Volume and Issue: 23(2), P. 410 - 415

Published: Jan. 5, 2021

The indole scaffold is a ubiquitous and useful substructure, extensive investigations have been conducted to construct the framework and/or realize modification. Nevertheless, direct selective functionalization on benzenoid core must overcome high activity of C-3 position still remains highly challenging. Herein, palladium-catalyzed specific C-7 acylation indolines in presence an easily removed directing group was developed. This strategy usually considered as practical for preparation acylated indoles because indoline can be converted under oxidation conditions. In particular, our greatly improved alkacylation yield which only unsatisfactory could achieved previous studies. Furthermore, reaction scaled up gram level standard conditions with much lower palladium loading (1 mol %).

Language: Английский

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Rhoda‐Electrocatalyzed Bimetallic C−H Oxygenation by Weak O‐Coordination

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(24), P. 13264 - 13270

Published: March 2, 2021

Rhodium-electrocatalyzed arene C-H oxygenation by weakly O-coordinating amides and ketones have been established bimetallic electrocatalysis. Likewise, diverse dihydrooxazinones were selectively accessed the judicious choice of current, enabling twofold functionalization. Detailed mechanistic studies experiment, mass spectroscopy cyclovoltammetric analysis provided support for an unprecedented electrooxidation-induced activation a rhodium catalysis manifold.

Language: Английский

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Ruthenium‐Catalyzed C7‐Formylmethylation or Sequential Acetalization of Indolines with Vinylene Carbonate in Different Solvents

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(9), P. 1580 - 1586

Published: April 1, 2022

Abstract The ruthenium‐catalyzed C7‐formylmethylation or sequential acetalization of indolines with vinylene carbonate has been realized under simple and easy‐to‐operate reaction systems. Several preliminary mechanistic studies derivatization reactions for the conversion formylmethyl group were also performed. This transformation offers an alternative approach direct C( sp 2 )−H to corresponding acetal structure. magnified image

Language: Английский

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RhRu Bimetallic Oxide Cluster Catalysts for Cross-Dehydrogenative Coupling of Arenes and Carboxylic Acids

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19059 - 19069

Published: June 6, 2024

Noble-metal-based bimetallic oxide clusters are promising novel catalysts. In this study, we developed carbon-supported RhRu (RhRuO

Language: Английский

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Rhodium‐Catalyzed Direct and Selective ortho C−H Chalcogenation of N‐(Hetero)aryl‐7‐azaindoles

Advanced Synthesis & Catalysis, Journal Year: 2018, Volume and Issue: 360(12), P. 2291 - 2296

Published: April 12, 2018

Abstract Rhodium catalyzed synthesis of chalcogenated N ‐aryl‐7‐azaindoles/azaindolines has been developed through N‐directed ortho C sp 2 −H activation in presence silver triflate and carbonate 1,4‐dioxane using dichalcogenides. We have established this methodology as being efficient, highly regioselective scalable, having a broad substrates scope. Through route, range furnished thiolation selenylation azaindoles azaindolines good to excellent yields. These molecules could potential application biological and/or material science. magnified image

Language: Английский

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Cu-Catalyzed Direct C7 Sulfonylation of Indolines with Arylsulfonyl Chlorides

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 85(2), P. 1022 - 1032

Published: Dec. 13, 2019

An efficient Cu-catalyzed direct sulfonylation of indolines with easily accessible sulfonyl chlorides has been realized under an air atmosphere via a chelation-assisted strategy. This protocol exhibits several unique characteristics, including broad substrate scope, good functional group tolerance, and operational convenience, which enable regioselective access to variety C-7 functionalized indoline scaffolds in moderate yields. The mechanistic study reveals that the radical might be involved this transformation.

Language: Английский

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Ruthenium-Catalyzed Electrochemical Synthesis of Indolines through Dehydrogenative [3 + 2] Annulation with H₂ Evolution

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(21), P. 13735 - 13746

Published: Oct. 13, 2020

A dehydrogenative [3 + 2] annulation reaction of aniline derivatives and alkenes has been developed via the ruthenium-electron catalytic systems for synthesis versatile indolines. Electricity is used as a sustainable oxidant to regenerate active Ru(II) catalyst promote H2 evolution. This protocol ecofriendly easy handle it uses simple undivided cell in mild conditions without employment metal oxidants.

Language: Английский

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