3d Transition Metals for C–H Activation

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 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.

Language: Английский

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Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C Bonds

Chemical Reviews, Journal Year: 2015, Volume and Issue: 115(17), P. 9587 - 9652

Published: Aug. 13, 2015

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTEnantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C BondsAlan H. Cherney, Nathaniel T. Kadunce, Sarah E. Reisman*View Author Information The Warren Katharine Schlinger Laboratory for Chemistry Chemical Engineering, Division California Institute Technology, Pasadena, 91125, United States*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 17, 9587–9652Publication Date (Web):August 13, 2015Publication History Received17 March 2015Published online13 August inissue 9 September 2015https://doi.org/10.1021/acs.chemrev.5b00162Copyright © 2015 American SocietyRIGHTS & PERMISSIONSACS AuthorChoiceArticle Views40232Altmetric-Citations603LEARN 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 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 InReddit (12 MB) Get e-AlertsSUBJECTS:Cross coupling reaction,Electrophiles,Ligands,Reagents,Substitution reactions e-Alerts

Language: Английский

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Iron-Catalyzed C–H Bond Activation

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 9086 - 9139

Published: April 5, 2017

Catalytic C-H bond activation, which was an elusive subject of chemical research until the 1990s, has now become a standard synthetic method for formation new C-C and C-heteroatom bonds. The potential activation first described ruthenium catalysis is widely exploited by use various precious metals. Driven increasing interest in utilization ubiquitous metals that are abundant nontoxic, iron rapidly growing area research, iron-catalyzed been most actively explored recent years. In this review, we summarize development stoichiometric long history, catalytic functionalization, emerged about 10 years ago. We focus review on reactions take place via reactive organoiron intermediates, excluded those as Lewis acid or radical initiator. contents categorized type cleaved formed thereafter, it covers simple substrates possessing directing group anchors catalyst to substrate, providing overview iron-mediated reported literature October 2016.

Language: Английский

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The Complementary Competitors: Palladium and Copper in C–N Cross-Coupling Reactions

Organometallics, Journal Year: 2012, Volume and Issue: 31(22), P. 7753 - 7808

Published: Nov. 14, 2012

The C–N cross-coupling chemistry intensely developed since the late 1990s has supplied synthesists with an overwhelming number of methods to effectively combine carbon and nitrogen residues. This new relies on complexes mainly two metals, copper palladium, used as catalysts or stoichiometric agents. development revealed both similarities differences in principles for design catalytic systems analysis their reactivity selectivity. discussion these metals can be performed within a common mechanistic paradigm, helping elucidate key factors governing behavior transition-metal involved.

Language: Английский

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The role of organometallic copper(iii) complexes in homogeneous catalysis

Chemical Science, Journal Year: 2013, Volume and Issue: 4(6), P. 2301 - 2301

Published: Jan. 1, 2013

Organometallic CuIII species have been invoked in many copper-catalyzed reactions, but until recently, experimental evidences were lacking. The advent of new spectroscopic techniques and the characterization simple stable catalyst models key to gain clear mechanistic insights into these important reactions. In this perspective, we will discuss discoveries corresponding proposals that derive from reactions such as nucleophilic organocuprate chemistry for C–C bond formation, C–heteroatom cross-coupling (Ullmann condensation halide-exchange processes) direct C–H functionalizations catalyzed by copper.

Language: Английский

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Reactivity of Gold Complexes towards Elementary Organometallic Reactions

Angewandte Chemie International Edition, Journal Year: 2015, Volume and Issue: 54(50), P. 15022 - 15045

Published: Nov. 13, 2015

Abstract For a while, the reactivity of gold complexes was largely dominated by their Lewis acid behavior. In contrast to other transition metals, elementary steps organometallic chemistry—oxidative addition, reductive elimination, transmetallation, migratory insertion—have scarcely been studied in case or even remained unprecedented until recently. However, within last few years, ability undergo these fundamental reactions has unambiguously demonstrated, and shown extend well beyond π‐activation. this Review, main achievements described area are presented historical context. Particular emphasis is set on mechanistic studies structure determination key intermediates. The electronic structural parameters delineating discussed, as remaining challenges.

Language: Английский

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Copper-Catalyzed sp³ C–H Amination

Organometallics, Journal Year: 2012, Volume and Issue: 31(22), P. 7728 - 7752

Published: Nov. 14, 2012

Among the transition metals, copper-based catalyst systems enable widest range of N-containing reagents in C–H amination to allow for direct incorporation versatile N-based functionalities via ubiquitous bonds. In addition nitrene-based approaches involving sulfonyliminoiodinanes (PhI═NSO2R), diverse non-nitrene protocols have been developed that use organic amides, nitrosoarenes, and hydroxylamines, strained heterocycles such as oxaziridines, acetonitrile, secondary sulfonylamines, even alkylamines arylamines. Synthetic, mechanistic, theoretical studies reveal discrete copper nitrenes [Cu]═NR amides [Cu]–NHR be key reactive intermediates amination. Copper-catalyzed sp3 is reviewed, connecting catalytic reactivity patterns with likely wherever possible, goal stimulate further development functionalization reactions which possess significant sustainability advantages over other contemporary noble metals.

Language: Английский

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Enantioselective Formation of Quaternary Centers by Allylic Alkylation with First-Row Transition-Metal Catalysts

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(7), P. 4084 - 4099

Published: Feb. 11, 2021

Asymmetric allylic alkylation mediated by transition metals provides an efficient strategy to form quaternary stereogenic centers. While this transformation is dominated the use of second- and third-row (e.g., Pd, Rh, Ir), recent developments have revealed potential first-row metals, which provide not only a less expensive potentially equally alternative but also new mechanistic possibilities. This review summarizes examples for assembly stereocenters using prochiral substrates hard, achiral nucleophiles in presence copper complexes highlights complementary approaches with soft, catalyzed chiral cobalt nickel complexes.

Language: Английский

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Vinyl Epoxides in Organic Synthesis

Chemical Reviews, Journal Year: 2014, Volume and Issue: 114(16), P. 8037 - 8128

Published: April 29, 2014

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTVinyl Epoxides in Organic SynthesisJiayun He, Jesse Ling, and Pauline Chiu*View Author Information Department of Chemistry State Key Laboratory Synthetic Chemistry, The University Hong Kong, Pokfulam Road, Kong*E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 16, 8037–8128Publication Date (Web):April 29, 2014Publication History Received13 December 2013Published online29 April 2014Published inissue 27 August 2014https://pubs.acs.org/doi/10.1021/cr400709jhttps://doi.org/10.1021/cr400709jreview-articleACS PublicationsCopyright © 2014 American Chemical SocietyRequest reuse permissionsArticle Views14124Altmetric-Citations227LEARN 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 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:Alcohols,Cyclization,Ethers,Substitution reactions,Vinyl Get e-Alerts

Language: Английский

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Facile Oxidative Addition of Aryl Iodides to Gold(I) by Ligand Design: Bending Turns on Reactivity

Journal of the American Chemical Society, Journal Year: 2014, Volume and Issue: 136(42), P. 14654 - 14657

Published: Sept. 30, 2014

Thanks to rational ligand design, the first gold(I) complexes undergo oxidative addition of aryl iodides were discovered. The reaction proceeds under mild conditions and is general. ensuing gold(III) have been characterized by spectroscopic crystallographic means. DFT calculations indicate that bending induced diphosphine plays a key role in this process.

Language: Английский

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