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 Cross-Couplings through Carbene Migratory Insertion

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(23), P. 13810 - 13889

Published: Nov. 1, 2017

Transition-metal-catalyzed cross-coupling reactions have been well-established as indispensable tools in modern organic synthesis. One of the major research goals area is expanding scope coupling partners. In past decade, diazo compounds (or their precursors N-tosylhydrazones) emerged nucleophilic partners C-C single bond or C═C double formations transition-metal-catalyzed reactions. This type reaction involves following general steps. First, organometallic species generated by various processes, including oxidative addition, transmetalation, cyclization, cleavage, and C-H activation. Subsequently, reacts with substrate to generate metal carbene intermediate, which undergoes rapid migratory insertion form a bond. The new from may undergo transformations. carbene-based has proven be general: transition metals Pd, Cu, Rh, Ni, Co, Ir are effective catalysts; also extended substrates other than compounds; cascade processes devised based on insertion. review will summarize achievements made this field since 2001.

Language: Английский

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Substrate Activation Strategies in Rhodium(III)-Catalyzed Selective Functionalization of Arenes

Accounts of Chemical Research, Journal Year: 2015, Volume and Issue: 48(4), P. 1007 - 1020

Published: April 6, 2015

The possibility of developing new methods for the efficient construction organic molecules via disconnections other than traditional functional group transformations has driven interest in direct functionalization C-H bonds. ubiquity bonds makes such attractive, but they also pose several challenges. first is reactivity and selectivity To achieve this, directing groups (DGs) are often installed that can enhance effective concentration catalyst, leading to thermodynamically stable metallacyclic intermediates. However, presence a pendant product undesirable unnecessary. This may account limitation applications reactions more common general uses. Thus, development removable or functionalizable desirable. Another key problem resulting M-C bond be low, which limit scope coupling partners hence reaction patterns activation reactions. While Cp*Rh(III)-catalyzed arenes was reported only 7 years ago, significant progress been made this area past few years. We began our studies 2010, we others have demonstrated diversified catalytic realized using Cp*Rh(III) complexes with high reactivity, stability, compatibility. Account describes efforts solve some these challenges Rh(III) catalysis. fulfilled design arene substrates by taking advantage nucleophilicity, electrophilicity, oxidizing potential, properties participating ligand when coupled relatively reactive unsaturated as alkenes alkynes. These situ funtionalizable roles DG allowed extensive chemical manipulation initial product, especially diverse array heterocycles. In polar partners, Rh(III)-C(aryl) showed higher both an organometallic reagent nucleophilic aryl source. were accordingly activated virtue umpolung, ring strain, rearomatization. All possible integration compatibility Rh(III)-C into systems. date achieved under rhodium addition, means stoichiometric reactions, gained mechanistic insights interactions between Rh-C opened avenues future

Language: Английский

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Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

Chemical Reviews, Journal Year: 2015, Volume and Issue: 115(21), P. 12045 - 12090

Published: Oct. 1, 2015

ADVERTISEMENT RETURN TO ISSUEPREVReviewTransition-Metal-Catalyzed Cleavage of C–N Single BondsKunbing Ouyang†‡, Wei Hao†, Wen-Xiong Zhang*†§, and Zhenfeng Xi†View Author Information† Beijing National Laboratory for Molecular Sciences (BNLMS), Key Bioorganic Chemistry Engineering the Ministry Education, College Chemistry, Peking University, 100871, China‡ Institute Chinese Academy (CAS), 100190, China§ State Elemento-Organic Nankai Tianjin 300071, China*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 21, 12045–12090Publication Date (Web):October 1, 2015Publication History Received3 July 2015Published online1 October inissue 11 November 2015https://pubs.acs.org/doi/10.1021/acs.chemrev.5b00386https://doi.org/10.1021/acs.chemrev.5b00386review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views26285Altmetric-Citations562LEARN ABOUT THESE METRICSArticle Views are COUNTER-compliant sum full text article downloads since 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated to reflect usage leading up last few days.Citations number other articles citing this article, calculated by Crossref daily. Find more information about citation counts.The Altmetric Attention Score is a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Amines,Bond cleavage,Cations,Oxidative addition,Salts Get e-Alerts

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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Cycloaddition reactions of enoldiazo compounds

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 46(17), P. 5425 - 5443

Published: Jan. 1, 2017

A comprehensive review on cycloaddition reactions of enoldiazo compounds is presented with emphasis methodology development and mechanistic insight.

Language: Английский

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Experimental and Theoretical Studies on Rhodium-Catalyzed Coupling of Benzamides with 2,2-Difluorovinyl Tosylate: Diverse Synthesis of Fluorinated Heterocycles

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(9), P. 3537 - 3545

Published: Feb. 8, 2017

Fluorinated heterocycles play an important role in pharmaceutical and agrochemical industries. Herein, we report on the synthesis of four types fluorinated via rhodium(III)-catalyzed C—H activation arenes/alkenes versatile coupling with 2,2-difluorovinyl tosylate. With N-OMe benzamide being a directing group (DG), reaction delivered monofluorinated alkene retention tosylate functionality. Subsequent one-pot acid treatment allowed efficient 4-fluoroisoquinolin-1(2H)-ones 5-fluoropyridin-2(1H)-ones. When N—OPiv benzamides were used, however, [4 + 2] cyclization occurred to provide gem-difluorinated dihydroisoquinolin-1(2H)-ones. Synthetic applications have been demonstrated ready availability both arene partner highlighted synthetic potentials these protocols. Mechanistically, two processes share common process involving N—H deprotonation, activation, olefin insertion form 7-membered rhodacycle. Thereafter, different pathways featuring β-F elimination C—N bond formation are followed basis density functional theory (DFT) studies. These DG-dependent led open chain products, respectively. The mechanistic rationale was supported by detailed DFT In particular, origins intriguing selectivity competing versus elucidated. It found that is facile event proceeds syn-coplanar transition state low energy barrier. migratory Rh—C(alkyl) into Rh(V) amido species. reactions, turnover-limiting, which stays good agreement experimental

Language: Английский

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Cross‐Coupling of α‐Carbonyl Sulfoxonium Ylides with C−H Bonds

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(42), P. 13117 - 13121

Published: Aug. 29, 2017

Abstract The functionalization of carbon–hydrogen bonds in non‐nucleophilic substrates using α‐carbonyl sulfoxonium ylides has not been so far investigated, despite the potential safety advantages that such reagents would provide over either diazo compounds or their situ precursors. Described herein are cross‐coupling reactions with C(sp 2 )−H arenes and heteroarenes presence a rhodium catalyst. reaction proceeds by succession C−H activation, migratory insertion ylide into carbon–metal bond, protodemetalation, last step being turnover‐limiting. method is applied to synthesis benz[c]acridines when allied an iridium‐catalyzed dehydrative cyclization.

Language: Английский

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Mechanistic view of Ru-catalyzed C–H bond activation and functionalization: computational advances

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(20), P. 7552 - 7576

Published: Jan. 1, 2018

Ru-Catalyzed aromatic C-H bond activation and functionalization have emerged as important topics because they resulted in remarkable progress organic synthesis. Both experimental theoretical studies of their mechanisms are for the design new synthetic methodologies. In this review, a mechanistic view Ru-mediated cleavage step is first given to reveal modes, including oxidative addition, metathesis base-assisted deprotonation. process, directing groups play an role determining reactivity bond. The generally leads formation Ru-C bond, which further functionalized subsequent steps. Ru-catalyzed arylation, alkylation, alkenylation arenes summarized, these transformations can be categorized into cross-coupling with electrophiles or coupling nucleophiles. mechanism ortho-ruthenation-enabled remote also discussed.

Language: Английский

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Mechanism of Rhodium-Catalyzed C–H Functionalization: Advances in Theoretical Investigation

Accounts of Chemical Research, Journal Year: 2017, Volume and Issue: 50(11), P. 2799 - 2808

Published: Nov. 7, 2017

ConspectusTransition-metal-catalyzed cross-coupling has emerged as an effective strategy for chemical synthesis. Within this area, direct C–H bond transformation is one of the most efficient and environmentally friendly processes construction new C–C or C–heteroatom bonds. Over past decades, rhodium-catalyzed functionalization attracted considerable attention because versatility wide use rhodium catalysts in chemistry. A series C–X (X = C, N, O) formation reactions could be realized from corresponding bonds using catalysts. Various experimental studies on have been reported, tandem, mechanistic computational also progressed significantly.Since 2012, our group performed theoretical to reveal mechanism reactions. We studied changes oxidation state compared Rh(I)/Rh(III) catalytic cycle Rh(III)/Rh(V) density functional theory calculation. The development advanced methods improvements computing power make calculation a powerful tool study Computational able not only provide insights but explain origin regioselectivity, enantioselectivity, stereoselectivity reactions.This Account summarizes work under discussion divided into three main parts: cleavage step, C–Rh bond, regeneration active catalyst. In results four possible mechanisms, including concerted metalation–deprotonation (CMD), oxidative addition (OA), Friedel–Crafts-type electrophilic aromatic substitution (SEAr), σ-complex assisted metathesis (σ-CAM) are discussed. Subsequent example, via insertion CO, olefin, alkyne, carbene, nitrene, constructs For catalyst, reductive elimination high-valent complex protonation emphasized potential candidates. detailing reaction pathway, regioselectivity diastereoselectivity commented upon Account. selectivity clarified through analysis. Furthermore, we summarize compare along complete pathway. described demonstrates that catalysis might proceed Rh(I)/Rh(III), Rh(II)/Rh(IV), Rh(III)/Rh(V), non-redox-Rh(III) cycles.

Language: Английский

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