Carboxylate-Assisted Transition-Metal-Catalyzed C−H Bond Functionalizations: Mechanism and Scope

Chemical Reviews, Год журнала: 2011, Номер 111(3), С. 1315 - 1345

Опубликована: Март 9, 2011

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCarboxylate-Assisted Transition-Metal-Catalyzed C−H Bond Functionalizations: Mechanism and ScopeLutz Ackermann*View Author Information Institut für Organische und Biomolekulare Chemie, Georg-August-Universität, Tammannstrasse 2, 37077 Göttingen, Germany*Fax: (+49)551-39-6777. E-mail: [email protected]Cite this: Chem. Rev. 2011, 111, 3, 1315–1345Publication Date (Web):March 9, 2011Publication History Received2 December 2010Published online9 March 2011Published inissue 9 2011https://pubs.acs.org/doi/10.1021/cr100412jhttps://doi.org/10.1021/cr100412jreview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views35746Altmetric-Citations3100LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 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 for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Anions,Functionalization,Hydrocarbons,Metalation,Organic reactions Get e-Alerts

Язык: Английский

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Towards mild metal-catalyzed C–H bond activation

Chemical Society Reviews, Год журнала: 2011, Номер 40(9), С. 4740 - 4740

Опубликована: Янв. 1, 2011

Functionalizing traditionally inert carbon–hydrogen bonds represents a powerful transformation in organic synthesis, providing new entries to valuable structural motifs and improving the overall synthetic efficiency. C–H bond activation, however, often necessitates harsh reaction conditions that result functional group incompatibilities limited substrate scope. An understanding of mechanism rational design experimental have led significant improvement both selectivity applicability. This critical review summarizes discusses endeavours towards development mild activation methods wishes trigger more research this goal. In addition, we examine select examples complex natural product synthesis demonstrate utility functionalization (84 references).

Язык: Английский

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3d Transition Metals for C–H Activation

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2192 - 2452

Опубликована: Ноя. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Язык: Английский

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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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Beyond Directing Groups: Transition‐Metal‐Catalyzed CH Activation of Simple Arenes

Angewandte Chemie International Edition, Год журнала: 2012, Номер 51(41), С. 10236 - 10254

Опубликована: Сен. 20, 2012

The use of coordinating moieties as directing groups for the functionalization aromatic C-H bonds has become an established tool to enhance reactivity and induce regioselectivity. Nevertheless, with regard synthetic applicability activation, there is a growing interest in transformations which group can be fully abandoned, thus allowing direct simple benzene derivatives. However, this approach requires disclosure new strategies achieve control selectivity. In review, recent advances emerging field non-chelate-assisted activation are discussed, highlighting some most intriguing inspiring examples induction

Язык: Английский

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Carboxylate-Assisted Ruthenium-Catalyzed Alkyne Annulations by C–H/Het–H Bond Functionalizations

Accounts of Chemical Research, Год журнала: 2013, Номер 47(2), С. 281 - 295

Опубликована: Фев. 4, 2013

To improve the atom- and step-economy of organic syntheses, researchers would like to capitalize upon chemistry otherwise inert carbon–hydrogen (C–H) bonds. During past decade, remarkable progress in organometallic has set stage for development increasingly viable metal catalysts C–H bond activation reactions. Among these methods, oxidative functionalizations are particularly attractive because they avoid use prefunctionalized starting materials. For example, annulations that involve sequential heteroatom–H cleavages allow modular assembly regioselectively decorated heterocycles. These structures serve as key scaffolds natural products, functional materials, crop protecting agents, drugs. While other have devised rhodium or palladium complexes alkyne annulations, my laboratory focused on application significantly less expensive, yet highly selective ruthenium complexes.This Account summarizes evolution versatile ruthenium(II) alkynes via C–H/N–H, C–H/O–H, C–H/N–O cleavages. achieve functionalizations, we needed understand detailed mechanism crucial metalation with importance carboxylate assistance this process. As a consequence, our recent efforts resulted widely applicable methods preparation differently arenes heteroarenes, providing access among others isoquinolones, 2-pyridones, isoquinolines, indoles, pyrroles, α-pyrones. Most reactions used Cu(OAc)2·H2O, which not only acted oxidant but also served essential source acetate carboxylate-assisted ruthenation manifold. Notably, ruthenium(II)-catalyzed occurred under an ambient atmosphere air cocatalytic amounts Cu(OAc)2·H2O. Moreover, substrates displaying N–O bonds "internal oxidants" syntheses isoquinolones isoquinolines. Detailed experimental mechanistic studies provided strong support catalytic cycle relies initial ruthenation, followed by coordinative insertion alkyne, reductive elimination, reoxidation thus formed ruthenium(0) complex.

Язык: Английский

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Transition metal-catalyzed C–H bond functionalizations by the use of diverse directing groups

Organic Chemistry Frontiers, Год журнала: 2015, Номер 2(9), С. 1107 - 1295

Опубликована: Янв. 1, 2015

In this review, a summary of transition metal-catalyzed C–H activation by utilizing the functionalities as directing groups is presented.

Язык: Английский

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C–H functionalization logic in total synthesis

Chemical Society Reviews, Год журнала: 2011, Номер 40(4), С. 1976 - 1976

Опубликована: Янв. 1, 2011

In this critical review, the strategic and economic benefits of C-H functionalization logic will be analyzed through lens total synthesis. order to illustrate dramatically simplifying effects type can potentially have on synthetic planning, we take reader a series case studies in which it has already been successfully applied. first section, chronological look at key historical syntheses examined, leading into modern day examples. second our own experience with applying executing synthesis "mindset" discussed (114 references).

Язык: Английский

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If CH Bonds Could Talk: Selective CH Bond Oxidation

Angewandte Chemie International Edition, Год журнала: 2011, Номер 50(15), С. 3362 - 3374

Опубликована: Март 16, 2011

Abstract CH oxidation has a long history and an ongoing presence in research at the forefront of chemistry interrelated fields. As such, numerous highly useful articles reviews have been written on this subject. Logically, these are generally from perspective scope limitations reagents employed. This Minireview instead attempts to emphasize chemoselectivity imposed by nature substrate. Consequently, many landmark discoveries field not discussed, but hopefully taken herein will allow reactions be more readily incorporated into synthetic planning.

Язык: Английский

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Copper‐Catalyzed Aerobic Oxidative CH Functionalizations: Trends and Mechanistic Insights

Angewandte Chemie International Edition, Год журнала: 2011, Номер 50(47), С. 11062 - 11087

Опубликована: Окт. 27, 2011

The selective oxidation of C-H bonds and the use O(2) as a stoichiometric oxidant represent two prominent challenges in organic chemistry. Copper(II) is versatile oxidant, capable promoting wide range oxidative coupling reactions initiated by single-electron transfer (SET) from electron-rich molecules. Many these can be rendered catalytic Cu employing molecular oxygen to regenerate active copper(II) catalyst. Meanwhile, numerous other recently reported Cu-catalyzed feature substrates that are electron-deficient or appear unlikely undergo copper(II). In some cases, evidence has been obtained for involvement organocopper(III) intermediates reaction mechanism. Organometallic this type important new opportunities field aerobic oxidations.

Язык: Английский

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