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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Cooperative Coupling of Oxidative Organic Synthesis and Hydrogen Production over Semiconductor-Based Photocatalysts

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13051 - 13085

Published: Aug. 11, 2021

Merging hydrogen (H2) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H2 fuel and high-value chemicals can be coproduced under mild conditions using light as sole energy input. Following this dual-functional photocatalytic strategy, dreamlike pathway for constructing C–C/C–X (X = C, N, O, S) bonds from abundant readily available X–H bond-containing compounds concomitant release of fulfilled without need external chemical reagents, thus offering green fascinating synthetic strategy. In review, we begin by presenting concise overview on general background traditional production then focus fundamental principles cooperative coupling selective simultaneous utilization photoexcited electrons holes over semiconductor-based catalysts to meet economic sustainability goal. Thereafter, put dedicated emphasis recent key progress various transformations, including alcohol oxidation, methane conversion, amines coupling, cross-coupling, cyclic alkanes dehydrogenation, reforming lignocellulosic biomass, so on. Finally, remaining challenges future perspectives flourishing area have been critically discussed. It anticipated that review will provide enlightening guidance rational design such system, thereby stimulating development economical environmentally benign solar generation value-added fine chemicals.

Language: Английский

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Construction of Axially Chiral Compounds via Asymmetric Organocatalysis

Accounts of Chemical Research, Journal Year: 2018, Volume and Issue: 51(2), P. 534 - 547

Published: Feb. 8, 2018

ConspectusAxially chiral compounds have received much attention from chemists because of their widespread appearance in natural products, biologically active compounds, and useful ligands asymmetric catalysis. Because the importance this structural motif, catalytic enantioselective construction axially scaffolds has been intensively investigated, great progress accomplished. However, majority methodologies field focus on use metal catalysis, whereas approaches involving organocatalysis started to emerge only recently. This Account describes certain advances organocatalytic synthesis following strategies: kinetic resolution, desymmetrization, cyclization/addition, direct arylation, so on. We began our investigation by developing a highly efficient strategy for resolution BINAM derivatives Brønsted acid-catalyzed imine formation transfer hydrogenation cascade process, thereby providing convenient route generate high yields with excellent enantioselectivities. The desymmetrization 1-aryltriazodiones (ATADs) through an organocatalyzed tyrosine clicklike reaction wherein nucleophile was added ATAD afforded interesting type N-arylurazole remote enantiocontrolled manner. then focused cyclization addition given inherent limitations terms chemical yield substrate scope. By utilizing Paal–Knorr reaction, we disclosed general method access enantiomerically pure arylpyrroles. heterocycle stepwise method, which executed one-pot fashion containing subsequent aromatization, were successfully applied diverse arylquinazolinones catalyzed acids. discovered approach construct styrenes 1,4-addition arylalkynals good Such motifs are important precursors further transformations into synthetic intermediates may potential applications syntheses as olefin or organocatalysts. To tackle challenge, accomplished phosphoric arylative reactions 2-naphthol 2-naphthamine quinone deliver class BINOL NOBIN enantioselectivities under mild conditions. Most importantly, that azo group can effectively perform directing activating formal aryl C–H functionalization via nucleophilic aromatic substitution azobenzene derivatives. Thus, wide range arylindoles synthesized anticipate will foster development many other motivate new enthusiasm functionalization. Moreover, SPINOLs fundamental organocatalysts ligands. developed SPINOLs. is convergent functional-group-tolerant generation results, thus delivering practical privileged structure.

Language: Английский

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Recent Advances in Oxidative R¹-H/R²-H Cross-Coupling with Hydrogen Evolution via Photo-/Electrochemistry

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(12), P. 6769 - 6787

Published: May 10, 2019

Photo-/electrochemical catalyzed oxidative R1-H/R2-H cross-coupling with hydrogen evolution has become an increasingly important issue for molecular synthesis. The dream of construction C-C/C-X bonds from readily available C-H/X-H release H2 can be facilely achieved without external chemical oxidants, providing a greener model bond formation. Given the great influence these reactions in organic chemistry, we give summary state art via photo/electrochemistry, and hope this review will stimulate development synthetic strategy near future.

Language: Английский

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Recent advances in the synthesis of axially chiral biarylsviatransition metal-catalysed asymmetric C–H functionalization

Chemical Communications, Journal Year: 2019, Volume and Issue: 55(59), P. 8514 - 8523

Published: Jan. 1, 2019

Recent advances in the synthesis of axially chiral biarylsviatransition metal-catalysed asymmetric C–H functionalization are reported.

Language: Английский

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Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp³)–H Bonds

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(24), P. 14957 - 15074

Published: Oct. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Language: Английский

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Photoinduced Remote Functionalisations by Iminyl Radical Promoted C−C and C−H Bond Cleavage Cascades

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 57(3), P. 744 - 748

Published: Nov. 8, 2017

Abstract A photoinduced cascade strategy leading to a variety of differentially functionalised nitriles and ketones has been developed. These reactions rely on the oxidative generation iminyl radicals from simple oximes. Radical transposition by C(sp 3 )−(sp ) )−H bond cleavage gives access distal carbon that undergo S H 2 functionalisations. mild, visible‐light‐mediated procedures can be used for remote fluorination, chlorination, azidation, were applied modification bioactive structurally complex molecules.

Language: Английский

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50th Anniversary Perspective: Living Polymerization—Emphasizing the Molecule in Macromolecules

Macromolecules, Journal Year: 2017, Volume and Issue: 50(18), P. 6979 - 6997

Published: Sept. 17, 2017

The ideal of living polymerization has defined research in polymer chemistry over the past 50 years. In this Perspective, we present case that concept enabled treatment polymers as organic molecules, rather than impure mixtures species, and allowed translation methods developed by synthetic chemists into ever more accessible and/or controlled methods. concurrent development rapid analytical for screening new characteristics, chiefly size exclusion chromatography, greatly aided expansion

Language: Английский

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Introduction: CH Activation

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 8481 - 8482

Published: July 12, 2017

ADVERTISEMENT RETURN TO ISSUEEditorialNEXTIntroduction: CH ActivationRobert H. Crabtree and Aiwen LeiView Author Information Yale University Wuhan UniversityCite this: Chem. Rev. 2017, 117, 13, 8481–8482Publication Date (Web):July 12, 2017Publication History Published online12 July 2017Published inissue 12 2017https://pubs.acs.org/doi/10.1021/acs.chemrev.7b00307https://doi.org/10.1021/acs.chemrev.7b00307editorialACS PublicationsCopyright © 2017 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions free to access through this site. Learn MoreArticle Views39442Altmetric-Citations261LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated reflect usage leading up last few days.Citations number other articles citing article, calculated by Crossref daily. Find more information about citation counts.The Altmetric Attention Score 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 for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail (2 MB) Get e-AlertscloseSUBJECTS:Alcohols,Functionalization,Hydrocarbons,Metals,Palladium e-Alerts

Language: Английский

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Transition Metal‐Catalyzed Enantioselective C−H Functionalization via Chiral Transient Directing Group Strategies

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(45), P. 19773 - 19786

Published: July 20, 2020

Abstract Transition metal‐catalyzed enantioselective functionalization of C−H bond, the most abundant functionality in organic molecules, has emerged as an expedient synthetic approach to streamline synthesis complex chiral molecules. Despite significant progress, traditional directing group‐enabled strategies require additional steps for installation and removal groups from target molecule. The recently developed asymmetric using transient ( c TDGs) offers a promising alternative that can circumvent this obstacle therefore simplify process. In Minireview, we briefly discuss advent recent advances emerging concept, with emphasis on discussing creation various stereogenic centers developments TDGs. Applications natural product ligand derivatizations are also discussed. We hope Minireview will highlight great potential strategy help inspire further endeavors.

Language: Английский

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