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Catalytic Cross-Coupling Reactions

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This cluster of papers focuses on the advances in transition metal-catalyzed cross-coupling reactions, particularly palladium-catalyzed processes, for organic synthesis. It covers topics such as C-C bond formation, homogeneous and heterogeneous catalysis, aryl halides, Suzuki-Miyaura and Heck reactions, and the use of nickel as a catalyst.

Keywords

Palladium-Catalyzed; Cross-Coupling Reactions; Transition Metal Catalysis; Organic Synthesis; C-C Bond Formation; Homogeneous and Heterogeneous Catalysis; Aryl Halides; Suzuki-Miyaura Reaction; Heck Reaction; Nickel-Catalyzed

Metal‐Catalyzed Cross‐Coupling Reactions

2004-08-25

Armin de Meijere , François Diederich

Preface.List of Contributors.1 Mechanistic Aspects of Metal-Catalyzed C,C- and C,X-Bond-Forming Reactions (Antonio M. Echavarren and Diego J. Cardenas).1.1 Mechanisms of Cross-Coupling Reactions.1.2 Formation of C,C-Bonds in the Palladium-Catalyzed alpha-Arylation of … Preface.List of Contributors.1 Mechanistic Aspects of Metal-Catalyzed C,C- and C,X-Bond-Forming Reactions (Antonio M. Echavarren and Diego J. Cardenas).1.1 Mechanisms of Cross-Coupling Reactions.1.2 Formation of C,C-Bonds in the Palladium-Catalyzed alpha-Arylation of Carbonyl Compounds and Nitriles.1.3 Key Intermediates in the Formation of C-X (X = N, O, S) bonds in Metal-Catalyzed Reactions 251.3.1 Reductive Elimination of C-N, C-O, and C-S Bonds From Organopalladium(II) Complexes.1.4 Summary and Outlook.Abbreviations.References.2 Metal-Catalyzed Cross-Coupling Reactions of Organoboron Compounds with Organic Halides (Norio Miyaura).2.1 Introduction.2.2 Advances in the Synthesis of Organoboron Compounds.2.3 Reaction Mechanism.2.4 Reaction Conditions.2.5 Side Reactions.2.6 Reactions of B-Alkyl Compounds.2.7 Reactions of B-Alkenyl Compounds.2.8 Reactions of B-Aryl Compounds.2.9 Reactions of B-Allyl and B-Alkynyl Compounds.2.10 Reactions Giving Ketones.2.11 Dimerization of Arylboronic Acids.2.12 N-, O-, and S-Arylation.Abbreviations.References.3 Organotin Reagents in Cross-Coupling Reactions (Terence N. Mitchell).3.1 Introduction.3.2 Mechanism and Methodology.3.3 Natural Product Synthesis.3.4 Organic Synthesis.3.5 Polymer Chemistry.3.6 Inorganic Synthesis.3.7 Conclusions.3.8 Experimental Procedures.Abbreviations.References.4 Organosilicon Compounds in Cross-Coupling Reactions (Scott E. Denmark and Ramzi F. Sweis).4.1 Introduction.4.2 Modern Organosilicon-Cross-Coupling.4.3 Mechanistic Studies in Silicon-Cross-Coupling.4.4 Applications to Total Synthesis.4.5 Summary and Outlook.4.6 Experimental Procedures.Abbreviations.References.5 Cross-Coupling of Organyl Halides with Alkenes: The Heck Reaction (Stefan Brase and Armin de Meijere).5.1 Introduction.5.2 Principles.5.3 Cascade Reactions and Multiple Couplings.5.4 Related Palladium-Catalyzed Reactions.5.5 Enantioselective Heck-Type Reactions.5.6 Syntheses of Heterocycles, Natural Products and Other Biologically Active Compounds Applying Heck Reactions.5.7 Carbopalladation Reactions in Solid-Phase Syntheses.5.8 The Heck Reaction in Fine Chemicals Syntheses.5.9 Conclusions.5.10 Experimental Procedures.Acknowledgments.Abbreviations and Acronyms.References.6 Cross-Coupling Reactions to sp Carbon Atoms (Jeremiah A. Marsden and Michael M. Haley).6.1 Introduction.6.2 Alkynylcopper Reagents.6.3 Alkynyltin Reagents.6.4 Alkynylzinc Reagents.6.5 Alkynylboron Reagents.6.6 Alkynylsilicon Reagents.6.7 Alkynylmagnesium Reagents.6.8 Other Alkynylmetals.6.9 Concluding Remarks.6.10 Experimental Procedures.Acknowledgments.Abbreviations and Acronyms.References.7 Carbometallation Reactions (Ilan Marek, Nicka Chinkov, and Daniella Banon-Tenne).7.1 Introduction.7.2 Carbometallation Reactions of Alkynes.7.3 Carbometallation Reactions of Alkenes.7.4 Zinc-Enolate Carbometallation Reactions.7.5 Carbometallation Reactions of Dienes and Enynes.7.6 Carbometallation Reactions of Allenes.7.7 Conclusions.7.8 Experimental Procedures.Acknowledgments.References.8 Palladium-Catalyzed 1,4-Additions to Conjugated Dienes (Jan-E. Backvall).8.1 Introduction.8.2 Palladium(0)-Catalyzed Reactions.8.3 Palladium(II)-Catalyzed Reactions.References.9 Cross-Coupling Reactions via PI-Allylmetal Intermediates (Uli Kazmaier and Matthias Pohlman)9.1 Introduction.9.2 Palladium-Catalyzed Allylic Alkylations.9.3 Allylic Alkylations with Other Transition Metals.9.4 Experimental Procedures.Abbreviations.References.10 Palladium-Catalyzed Coupling Reactions of Propargyl Compounds (Jiro Tsuji and Tadakatsu Mandai).10.1 Introduction.10.2 Classification of Pd-Catalyzed Coupling Reactions of Propargyl Compounds.10.3 Reactions with Insertion into the sp2 Carbon Bond of Allenylpalladium Intermediates (Type I).10.4 Transformations via Transmetallation of Allenylpalladium Intermediates and Related Reactions (Type II).10.5 Reactions with Attack of Soft Carbon and Oxo Nucleophiles on the sp-Carbon of Allenylpalladium Intermediates (Type III).10.6 Experimental Procedures.Abbreviations.References.11 Carbon-Carbon Bond-Forming Reactions Mediated by Organozinc Reagents (Paul Knochel, M. Isabel Calaza, and Eike Hupe).11.1 Introduction.11.2 Methods of Preparation of Zinc Organometallics.11.3 Uncatalyzed Cross-Coupling Reactions.11.4 Copper-Catalyzed Cross-Coupling Reactions.11.5 Transition Metal-Catalyzed Cross-Coupling Reactions.11.6 Conclusions.11.7 Experimental Procedures.Abbreviations.References.12 Carbon-Carbon Bond-Forming Reactions Mediated by Organomagnesium Reagents (Paul Knochel, Ioannis Sapountzis, and Nina Gommermann).12.1 Introduction.12.2 Preparation of Polyfunctionalized Organomagnesium Reagents via a Halogen-Magnesium Exchange.12.3 Conclusions.12.4 Experimental Procedures.References.13 Palladium-Catalyzed Aromatic Carbon-Nitrogen Bond Formation (Lei Jiang and Stephen L. Buchwald).13.1 Introduction.13.2 Mechanistic Studies.13.3 General Features.13.4 Palladium-Catalyzed C-N Bond Formation.13.5 Vinylation.13.6 Amination On Solid Support.13.7 Conclusion.13.8 Representative Experimental Procedures.References.14 The Directed ortho-Metallation (DoM) Cross-Coupling Nexus. Synthetic Methodology for the Formation of Aryl-Aryl and Aryl-Heteroatom-Aryl Bonds (Eric J.-G. Anctil and Victor Snieckus).14.1 Introduction.14.2 The Aim of this Chapter.14.3 Synthetic Methodology derived from the DoM-Cross-Coupling Nexus.14.4 Applications of DoM in Synthesis.14.5 Conclusions and Prognosis.14.6 Selected Experimental Procedures.Abbreviations.References and Notes.15 Palladium- or Nickel-Catalyzed Cross-Coupling with Organometals Containing Zinc, Aluminum, and Zirconium: The Negishi Coupling (Ei-ichi Negishi, Xingzhong Zeng, Ze Tan, Mingxing Qian, Qian Hu, and Zhihong Huang).15.1 Introduction and General Discussion of Changeable Parameters.15.2 Recent Developments in the Negishi Coupling and Related Pd- or Ni-Catalyzed Cross-Coupling Reactions.15.3 Summary and Conclusions.15.4 Representative Experimental Procedures.References.Index.

Advances in Transition Metal (Pd,Ni,Fe)-Catalyzed Cross-Coupling Reactions Using Alkyl-organometallics as Reaction Partners

2011-02-14

Ranjan Jana , Tejas P. Pathak , Matthew S. Sigman

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTAdvances in Transition Metal (Pd,Ni,Fe)-Catalyzed Cross-Coupling Reactions Using Alkyl-organometallics as Reaction PartnersRanjan Jana, Tejas P. Pathak, and Matthew S. Sigman*View Author Information Department of Chemistry, University of … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTAdvances in Transition Metal (Pd,Ni,Fe)-Catalyzed Cross-Coupling Reactions Using Alkyl-organometallics as Reaction PartnersRanjan Jana, Tejas P. Pathak, and Matthew S. Sigman*View Author Information Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112-8500, United States*E-mail: [email protected]Cite this: Chem. Rev. 2011, 111, 3, 1417–1492Publication Date (Web):February 14, 2011Publication History Received26 September 2010Published online14 February 2011Published inissue 9 March 2011https://pubs.acs.org/doi/10.1021/cr100327phttps://doi.org/10.1021/cr100327preview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views59492Altmetric-Citations1857LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Alkyls,Anions,Chemical reactions,Cross coupling reaction,Reagents Get e-Alerts

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The Potential of Palladacycles: More Than Just Precatalysts

2005-05-20

Jaı̈rton Dupont , Crestina S. Consorti , John Spencer

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Potential of Palladacycles: More Than Just PrecatalystsJairton Dupont, Crestina S. Consorti, and John SpencerView Author Information Laboratory of Molecular Catalysis, Institute of Chemistry, UFRGS, Av. Bento … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Potential of Palladacycles: More Than Just PrecatalystsJairton Dupont, Crestina S. Consorti, and John SpencerView Author Information Laboratory of Molecular Catalysis, Institute of Chemistry, UFRGS, Av. Bento Gonçalves, 9500 Porto Alegre, 91501-970 RS, Brazil, and James Black Foundation, 68 Half Moon Lane, London SE24 9JE, England Cite this: Chem. Rev. 2005, 105, 6, 2527–2572Publication Date (Web):May 20, 2005Publication History Received21 February 2005Published online20 May 2005Published inissue 1 June 2005https://pubs.acs.org/doi/10.1021/cr030681rhttps://doi.org/10.1021/cr030681rresearch-articleACS PublicationsCopyright © 2005 American Chemical SocietyRequest reuse permissionsArticle Views11895Altmetric-Citations1214LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Catalysts,Heck reaction,Hydrocarbons,Ligands,Palladium Get e-Alerts

Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis

2002-11-01

Sambasivarao Kotha , Kakali Lahiri , Dhurke Kashinath

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Versatile Catalysts for the Suzuki Cross-Coupling of Arylboronic Acids with Aryl and Vinyl Halides and Triflates under Mild Conditions

2000-04-15

Adam F. Littke , Chaoyang Dai , Gregory C. Fu

Through the use of Pd2(dba)3/P(t-Bu)3 as a catalyst, a wide range of aryl and vinyl halides, including chlorides, undergo Suzuki cross-coupling with arylboronic acids in very good yield, typically at … Through the use of Pd2(dba)3/P(t-Bu)3 as a catalyst, a wide range of aryl and vinyl halides, including chlorides, undergo Suzuki cross-coupling with arylboronic acids in very good yield, typically at room temperature; through use of Pd(OAc)2/PCy3, a diverse array of aryl and vinyl triflates react cleanly at room temperature. Together, these two catalyst systems cover a broad spectrum of commonly encountered substrates for Suzuki couplings. Furthermore, they display novel reactivity patterns, such as the selective cross-coupling by Pd2(dba)3/P(t-Bu)3 of an aryl chloride in preference to an aryl triflate, and they can be used at low loading, even for reactions of aryl chlorides. Preliminary mechanistic work indicates that a palladium monophosphine complex is the active catalyst in the cross-coupling of aryl halides.

Palladium-Catalyzed Coupling Reactions of Aryl Chlorides

2002-11-14

Adam F. Littke , Gregory C. Fu

Collectively, palladium-catalyzed coupling reactions represent some of the most powerful and versatile tools available to synthetic organic chemists. Their widespread popularity stems in part from the fact that they are … Collectively, palladium-catalyzed coupling reactions represent some of the most powerful and versatile tools available to synthetic organic chemists. Their widespread popularity stems in part from the fact that they are generally tolerant to a large number of functional groups, which allows them to be employed in a wide range of applications. However, for many years a major limitation of palladium-catalyzed coupling processes has been the poor reactivity of aryl chlorides, which from the standpoints of cost and availability are more attractive substrates than the corresponding bromides, iodides, and triflates. Traditional palladium/triarylphosphane catalysts are only effective for the coupling of certain activated aryl chlorides (for example, heteroaryl chlorides and substrates that bear electron-withdrawing groups), but not for aryl chlorides in general. Since 1998, major advances have been described by a number of research groups addressing this challenge; catalysts based on bulky, electron-rich phosphanes and carbenes have proved to be particularly mild and versatile. This review summarizes both the seminal early work and the exciting recent developments in the area of palladium-catalyzed couplings of aryl chlorides.

The Promise and Challenge of Iron-Catalyzed Cross Coupling

2008-06-28

Benjamin D. Sherry , Alois Fürstner

Transition metal catalysts, particularly those derived from the group VIII−X metals, display remarkable efficiency for the formation of carbon−carbon and carbon−heteroatom bonds through the reactions of suitable nucleophiles with organic … Transition metal catalysts, particularly those derived from the group VIII−X metals, display remarkable efficiency for the formation of carbon−carbon and carbon−heteroatom bonds through the reactions of suitable nucleophiles with organic electrophilic partners. Within this subset of the periodic table, palladium and nickel complexes offer the broadest utility, while additionally providing the deepest mechanistic insight into thus-termed "cross-coupling reactions". The mammoth effort devoted to palladium and nickel catalysts over the past 30 years has somewhat obscured reports of alternative metal complexes in this arena. As cross-coupling reactions have evolved into a critical support for modern synthetic chemistry, the search for alternative catalysts has been taken up with renewed vigor. When the current generation of synthetic chemists reflects back to the origins of cross coupling for inspiration, the well-documented effect of iron salts on the reactivity of Grignard reagents with organic electrophiles surfaces as a fertile ground for alternative catalyst development. Iron possesses the practical benefits more befitting an alkali or alkaline earth metal, while displaying the unique reactivity of a d-block element. Therefore the search for broadly applicable iron catalysts for cross coupling is an increasingly important goal in modern synthetic organic chemistry. This Account describes the evolution of iron-catalyzed cross coupling from its inception in the work of Kochi to the present. Specific emphasis is placed on reactivity and synthetic applications, with selected examples from acyl-, alkenyl-, aryl-, and alkyl halide/pseudohalide cross coupling included. The typical reaction partners are Grignard reagents, though organomanganese, -copper, and -zinc derivatives have also been used in certain cases. Such iron-catalyzed processes occur very rapidly even at low temperature and therefore are distinguished by broad functional group compatibility. Furthermore, recent advances in carbon−heteroatom bond formation and studies relevant to the general reactivity of in situ generated and structurally defined "low-valent" iron catalysts are presented. The preparative aspects of iron-catalyzed cross coupling are encouraging, but the inclination to classify these processes within the characteristic reaction manifold is premature, as mechanistic studies have evolved at a comparatively slow pace. A typical protocol for cross coupling employs an Fe(+2) or Fe(+3) precatalyst, which is reduced in situ by the organometallic nucleophile. The nature of the resulting active component(s) is still best described, more than 30 years later, in Kochi's original terms as a "reduced form of soluble iron". Despite huge gaps in our current knowledge, three distinct mechanisms have been formulated, largely based on empirical evidence: a "canonical" cross-coupling process, a manifold wherein alkylation of an organoiron intermediate replaces transmetalation as a key step, and finally a proposal reliant on the formation of nucleophilic ate complexes. Conjecture and speculation abound, but precisely what constitutes the catalytic cycle in iron-catalyzed cross coupling remains an extremely challenging unanswered question.

Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds

1995-11-01

Norio Miyaura , Akira Suzuki

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPalladium-Catalyzed Cross-Coupling Reactions of Organoboron CompoundsNorio. Miyaura and Akira. SuzukiCite this: Chem. Rev. 1995, 95, 7, 2457–2483Publication Date (Print):November 1, 1995Publication History Published online1 May 2002Published inissue … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPalladium-Catalyzed Cross-Coupling Reactions of Organoboron CompoundsNorio. Miyaura and Akira. SuzukiCite this: Chem. Rev. 1995, 95, 7, 2457–2483Publication Date (Print):November 1, 1995Publication History Published online1 May 2002Published inissue 1 November 1995https://pubs.acs.org/doi/10.1021/cr00039a007https://doi.org/10.1021/cr00039a007research-articleACS PublicationsRequest reuse permissionsArticle Views90442Altmetric-Citations11246LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

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The Palladium-Catalyzed Cross-Coupling Reaction of Phenylboronic Acid with Haloarenes in the Presence of Bases

1981-01-01

Norio Miyaura , Teiji Yanagi , Atsushi Suzuki

Abstract The transition metal-catalyzed reactions of organometallics with organic halides have been extensively studied to prove a new approach to selective formation of carbon-carbon bonds. Recently, such coupling reactions of … Abstract The transition metal-catalyzed reactions of organometallics with organic halides have been extensively studied to prove a new approach to selective formation of carbon-carbon bonds. Recently, such coupling reactions of haloarenes with aryl magnesium1–3 and zinc4 compounds in the presence of palladium or nickel complexes have been reported for the synthesis of biaryls. Davidson and Triggs5 have previously reported that arylboronic acids react with sodium palladate to give the corresponding biaryls in good yields. The synthetic utility of the dimerization reaction is, however, limited because it requires stoichiometric amounts of the palladium compound. On the other hand, we have recently reported that cross-coupling reactions between alkenylboranes and organic halides such as alkenyl,6 alkynyl,6 aryl,7 allyl,8 and benzyl8 halides are effectively catalyzed by a catalytic amount of tetrakis(triphenylphosphine)palladium, Pd(PPh3)4 in the presence of suitable bases as indicated in Scheme 1. Although the detailed mechanistic pathway is not clear at present, the reaction should involve a transmetallation step from alkenylboranes to alkenylpalladiums.

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The Heck Reaction as a Sharpening Stone of Palladium Catalysis

2000-07-21

I. P. Beletskaya , Andrei V. Cheprakov

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Heck Reaction as a Sharpening Stone of Palladium CatalysisIrina P. Beletskaya and Andrei V. CheprakovView Author Information Department of Chemistry, Moscow State University, 119899 Moscow, Russia … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Heck Reaction as a Sharpening Stone of Palladium CatalysisIrina P. Beletskaya and Andrei V. CheprakovView Author Information Department of Chemistry, Moscow State University, 119899 Moscow, Russia Cite this: Chem. Rev. 2000, 100, 8, 3009–3066Publication Date (Web):July 21, 2000Publication History Received10 January 2000Published online21 July 2000Published inissue 1 August 2000https://pubs.acs.org/doi/10.1021/cr9903048https://doi.org/10.1021/cr9903048research-articleACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views45669Altmetric-Citations3491LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Arylation,Catalysts,Heck reaction,Ligands,Palladium Get e-Alerts

Arylation of Olefin with Aryl Iodide Catalyzed by Palladium

1971-02-01

Tsutomu Mizoroki , Kunio Mori , Atsumu Ozaki

N-Heterocyclic carbene (NHC) ligands and palladium in homogeneous cross-coupling catalysis: a perfect union

2011-01-01

George C. Fortman , Steven P. Nolan

Cross-coupling reactions using Pd-NHC (NHC = N-heterocyclic carbene) catalysts are discussed in this critical review and examined in terms of catalytic activity and how these have permitted advances in the … Cross-coupling reactions using Pd-NHC (NHC = N-heterocyclic carbene) catalysts are discussed in this critical review and examined in terms of catalytic activity and how these have permitted advances in the area as they developed (95 references).

Palladium-Catalyzed Suzuki−Miyaura Cross-Coupling Reactions Employing Dialkylbiaryl Phosphine Ligands

2008-07-12

Rubén Martı́n , Stephen L. Buchwald

The cores of many types of polymers, ligands, natural products, and pharmaceuticals contain biaryl or substituted aromatic structures, and efficient methods of synthesizing these structures are crucial to the work … The cores of many types of polymers, ligands, natural products, and pharmaceuticals contain biaryl or substituted aromatic structures, and efficient methods of synthesizing these structures are crucial to the work of a broad spectrum of organic chemists. Recently, Pd-catalyzed carbon−carbon bond-forming processes, particularly the Suzuki−Miyaura cross-coupling reaction (SMC), have risen in popularity for this purpose. The SMC has many advantages over other methods for constructing these moieties, including mild conditions, high tolerance toward functional groups, the commercial availability and stability of its reagents, and the ease of handling and separating byproducts from its reaction mixtures. Until 1998, most catalysts for the SMC employed triarylphosphine ligands. More recently, new bulky and electron-rich phosphine ligands, which can dramatically improve the efficiency and selectivity of such cross-coupling reactions, have been introduced. In the course of our studies on carbon−nitrogen bond-forming reactions, we found that the use of electron-rich and bulky phosphines enhanced the rate of both the oxidative addition and reductive elimination processes; this was the beginning of our development of a new family of ligands, the dialkylbiarylphosphines L1−L12. These ligands can be used for a wide variety of palladium-catalyzed carbon−carbon, carbon−nitrogen, and carbon−oxygen bond-forming processes as well as serving as supporting ligands for a number of other reactions. The enhanced reactivity of these catalysts has expanded the scope of cross-coupling partners that can be employed in the SMC. With use of such dialkylbiarylphosphine ligands, the coupling of unactivated aryl chlorides, aryl tosylates, heteroaryl systems, and very hindered substrate combinations have become routine. The utility of these ligands has been successfully demonstrated in a wide number of synthetic applications, including industrially relevant processes. In this Account, we provide an overview of the use and impact of dialkylbiarylphosphine ligands in the SMC. We discuss our studies on the mechanistic framework of the reaction, which have allowed us to rationally modify the ligand structures in order to tune their properties. We also describe selected applications in the synthesis of natural products and new materials to illustrate the utility of these dialkylbiarylphosphine ligands in various "real-world" synthetic applications.

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N-Heterocyclic Carbenes in Late Transition Metal Catalysis

2009-07-09

Silvia Díez‐González , Nicolas Marion , Steven P. Nolan

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTN-Heterocyclic Carbenes in Late Transition Metal CatalysisSilvia Díez-González†, Nicolas Marion‡†, and Steven P. Nolan*†§View Author Information Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTN-Heterocyclic Carbenes in Late Transition Metal CatalysisSilvia Díez-González†, Nicolas Marion‡†, and Steven P. Nolan*†§View Author Information Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain, and School of Chemistry, University of St Andrews, North Haugh, St Andrews KY16 9ST, U.K.*[email protected]†Institute of Chemical Research of Catalonia.‡Present address: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139.§University of St Andrews.Cite this: Chem. Rev. 2009, 109, 8, 3612–3676Publication Date (Web):July 9, 2009Publication History Received24 February 2009Published online9 July 2009Published inissue 12 August 2009https://pubs.acs.org/doi/10.1021/cr900074mhttps://doi.org/10.1021/cr900074mreview-articleACS PublicationsCopyright © 2009 American Chemical SocietyRequest reuse permissionsArticle Views36042Altmetric-Citations2763LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Addition reactions,Catalysts,Chemical reactions,Hydrocarbons,Ligands Get e-Alerts

Palladium‐Catalyzed Cross‐Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize

2012-05-09

Carin C. C. Johansson Seechurn , Matthew O. Kitching , Thomas J. Colacot +1 more

In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki joined the prestigious circle of Nobel Laureate chemists for their roles in discovering and developing highly practical methodologies for C-C bond … In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki joined the prestigious circle of Nobel Laureate chemists for their roles in discovering and developing highly practical methodologies for C-C bond construction. From their original contributions in the early 1970s the landscape of the strategies and methods of organic synthesis irreversibly changed for the modern chemist, both in academia and in industry. In this Review, we attempt to trace the historical origin of these powerful reactions, and outline the developments from the seminal discoveries leading to their eminent position as appreciated and applied today.

Acetylenic Coupling: A Powerful Tool in Molecular Construction

2000-08-04

Peter Siemsen , R. C. Livingston , François Diederich

Acetylenic coupling is currently experiencing some of the most intensive study of its long history. Rigid and sterically undemanding di- and oligoacetylene moieties, which are frequently encountered in natural products, … Acetylenic coupling is currently experiencing some of the most intensive study of its long history. Rigid and sterically undemanding di- and oligoacetylene moieties, which are frequently encountered in natural products, are finding increasing application as key structural elements in synthetic receptors for molecular recognition. Interesting electronic and optical properties of extensively pi-conjugated systems have spurred research into new linear oligoalkynes and acetylenic carbon allotropes. The synthetic challenges associated with these efforts have in turn spawned new methods. While classical Glaser conditions are still frequently used for homocoupling, the demand for increasingly selective heterocoupling conditions has provided the focus of research over the past decades. These efforts have undoubtedly been hampered by a relatively poor mechanistic understanding of these processes. More recently, palladium-catalyzed coupling methods have led to improvements in both the selectivity and reliability of acetylenic homo- and heterocouplings and paved the way for their application to ever more complicated systems. The variety of acetylenic coupling protocols, the current mechanistic understanding, and their application in natural product and targeted synthesis are discussed comprehensively for the first time in this review, with an emphasis on the most recently developed methods, and their application to the synthesis of complex macromolecular structures.

The Palladium‐Catalyzed Cross‐Coupling Reactions of Organotin Reagents with Organic Electrophiles [New Synthetic Methods (58)]

1986-06-01

J. K. Stille

Abstract The cross‐coupling of organotin reagents with a variety of organic electrophiles, catalyzed by palladium, provides a novel method for generating a carbon‐carbon bond. Because this mild, versatile reaction is … Abstract The cross‐coupling of organotin reagents with a variety of organic electrophiles, catalyzed by palladium, provides a novel method for generating a carbon‐carbon bond. Because this mild, versatile reaction is tolerant of a wide variety of functional groups on either coupling partner, is stereospecific and regioselective, and gives high yields of product, it is ideal for use in the synthesis of elaborate organic molecules. When the coupling reaction is carried out in the presence of carbon monoxide, instead of a direct coupling, carbon monoxide insertion takes place, stitching the two coupling partners together and generating a ketone.

Nickel-Catalyzed Cross-Couplings Involving Carbon−Oxygen Bonds

2010-12-06

Brad M. Rosen , Kyle W. Quasdorf , Daniela A. Wilson +4 more

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTNickel-Catalyzed Cross-Couplings Involving Carbon−Oxygen BondsBrad M. Rosen†, Kyle W. Quasdorf‡, Daniella A. Wilson†, Na Zhang†, Ana-Maria Resmerita†, Neil K. Garg*‡, and Virgil Percec*†View Author Information† Roy & … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTNickel-Catalyzed Cross-Couplings Involving Carbon−Oxygen BondsBrad M. Rosen†, Kyle W. Quasdorf‡, Daniella A. Wilson†, Na Zhang†, Ana-Maria Resmerita†, Neil K. Garg*‡, and Virgil Percec*†View Author Information† Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States‡ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States*E-mail: [email protected]; [email protected]Cite this: Chem. Rev. 2011, 111, 3, 1346–1416Publication Date (Web):December 6, 2010Publication History Received12 August 2010Published online6 December 2010Published inissue 9 March 2011https://pubs.acs.org/doi/10.1021/cr100259thttps://doi.org/10.1021/cr100259treview-articleACS PublicationsCopyright © 2010 American Chemical SocietyRequest reuse permissionsArticle Views38290Altmetric-Citations1216LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Anions,Aromatic compounds,Catalysts,Cross coupling reaction,Homocouplings Get e-Alerts

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The Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry

2007-02-17

Rafael Chinchílla , Carmén Nájera

ADVERTISEMENT RETURN TO ISSUEPREVArticleThe Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry†Rafael Chinchilla and Carmen NájeraView Author Information Departamento de Química Orgánica and Instituto de Síntesis Orgánica (ISO), Universidad … ADVERTISEMENT RETURN TO ISSUEPREVArticleThe Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry†Rafael Chinchilla and Carmen NájeraView Author Information Departamento de Química Orgánica and Instituto de Síntesis Orgánica (ISO), Universidad de Alicante, Facultad de Ciencias, Apartado 99, 03080 Alicante, Spain Cite this: Chem. Rev. 2007, 107, 3, 874–922Publication Date (Web):February 17, 2007Publication History Received25 September 2006Published online17 February 2007Published inissue 1 March 2007https://pubs.acs.org/doi/10.1021/cr050992xhttps://doi.org/10.1021/cr050992xresearch-articleACS PublicationsCopyright © 2007 American Chemical SocietyRequest reuse permissionsArticle Views60007Altmetric-Citations2605LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Anions,Catalysts,Hydrocarbons,Palladium,Sonogashira coupling reaction Get e-Alerts

Catalytic CC, CN, and CO Ullmann‐Type Coupling Reactions

2009-08-13

Florian Monnier , Marc Taillefer

Copper-catalyzed Ullmann condensations are key reactions for the formation of carbon-heteroatom and carbon-carbon bonds in organic synthesis. These reactions can lead to structural moieties that are prevalent in building blocks … Copper-catalyzed Ullmann condensations are key reactions for the formation of carbon-heteroatom and carbon-carbon bonds in organic synthesis. These reactions can lead to structural moieties that are prevalent in building blocks of active molecules in the life sciences and in many material precursors. An increasing number of publications have appeared concerning Ullmann-type intermolecular reactions for the coupling of aryl and vinyl halides with N, O, and C nucleophiles, and this Minireview highlights recent and major developments in this topic since 2004.

Palladium(0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic Esters

1995-11-01

Tatsuo Ishiyama , Miki Murata , Norio Miyaura

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPalladium(0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic EstersTatsuo Ishiyama, Miki Murata, and Norio MiyauraCite this: J. Org. Chem. 1995, 60, 23, 7508–7510Publication … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPalladium(0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic EstersTatsuo Ishiyama, Miki Murata, and Norio MiyauraCite this: J. Org. Chem. 1995, 60, 23, 7508–7510Publication Date (Print):November 1, 1995Publication History Published online1 May 2002Published inissue 1 November 1995https://pubs.acs.org/doi/10.1021/jo00128a024https://doi.org/10.1021/jo00128a024research-articleACS PublicationsRequest reuse permissionsArticle Views35477Altmetric-Citations1355LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (2)»Supporting Information Supporting Information Get e-Alerts

Development of Pd–Cu catalyzed cross-coupling of terminal acetylenes with sp2-carbon halides

2002-07-01

Kenkichi Sonogashira

Copper-Mediated Coupling Reactions and Their Applications in Natural Products and Designed Biomolecules Synthesis

2008-08-01

Gwilherm Evano , Nicolas Blanchard , Mathieu Toumi

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCopper-Mediated Coupling Reactions and Their Applications in Natural Products and Designed Biomolecules SynthesisGwilherm Evano*†, Nicolas Blanchard*‡, and Mathieu Toumi†View Author Information Institut Lavoisier de Versailles, UMR CNRS … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCopper-Mediated Coupling Reactions and Their Applications in Natural Products and Designed Biomolecules SynthesisGwilherm Evano*†, Nicolas Blanchard*‡, and Mathieu Toumi†View Author Information Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint Quentin en Yvelines, 45 avenue des Etats-Unis, 78035 Versailles Cedex, France, and Laboratoire de Chimie Organique, Bioorganique et Macromoléculaire, UMR CNRS 7015, ENSCMu, Université de Haute-Alsace, 3 rue A. Werner, 68093 Mulhouse Cedex, France* Authors to whom correspondence should be addressed ([email protected], [email protected]).†Université de Versailles Saint Quentin en Yvelines.‡Université de Haute-Alsace.Cite this: Chem. Rev. 2008, 108, 8, 3054–3131Publication Date (Web):August 13, 2008Publication History Received7 July 2007Published online13 August 2008Published inissue 1 August 2008https://pubs.acs.org/doi/10.1021/cr8002505https://doi.org/10.1021/cr8002505review-articleACS PublicationsCopyright © 2008 American Chemical SocietyRequest reuse permissionsArticle Views36725Altmetric-Citations1897LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Anions,Aromatic compounds,Arylation,Cross coupling reaction,Organic synthesis Get e-Alerts

Recent advances in Sonogashira reactions

2011-01-01

Rafael Chinchílla , Carmén Nájera

The coupling of aryl or vinyl halides with terminal acetylenes catalysed by palladium and other transition metals, commonly termed as Sonogashira cross-coupling reaction, is one of the most important and … The coupling of aryl or vinyl halides with terminal acetylenes catalysed by palladium and other transition metals, commonly termed as Sonogashira cross-coupling reaction, is one of the most important and widely used sp(2)-sp carbon-carbon bond formation reactions in organic synthesis, frequently employed in the synthesis of natural products, biologically active molecules, heterocycles, molecular electronics, dendrimers and conjugated polymers or nanostructures. This critical review focuses on developments in the Sonogashira reaction achieved in recent years concerning catalysts, reaction conditions and substrates (352 references).

Palladium Complexes of N‐Heterocyclic Carbenes as Catalysts for Cross‐Coupling Reactions—A Synthetic Chemist's Perspective

2007-04-05

Eric Assen B. Kantchev , Christopher J. O’Brien , Michael G. Organ

Palladium-catalyzed C-C and C-N bond-forming reactions are among the most versatile and powerful synthetic methods. For the last 15 years, N-heterocyclic carbenes (NHCs) have enjoyed increasing popularity as ligands in … Palladium-catalyzed C-C and C-N bond-forming reactions are among the most versatile and powerful synthetic methods. For the last 15 years, N-heterocyclic carbenes (NHCs) have enjoyed increasing popularity as ligands in Pd-mediated cross-coupling and related transformations because of their superior performance compared to the more traditional tertiary phosphanes. The strong sigma-electron-donating ability of NHCs renders oxidative insertion even in challenging substrates facile, while their steric bulk and particular topology is responsible for fast reductive elimination. The strong Pd-NHC bonds contribute to the high stability of the active species, even at low ligand/Pd ratios and high temperatures. With a number of commercially available, stable, user-friendly, and powerful NHC-Pd precatalysts, the goal of a universal cross-coupling catalyst is within reach. This Review discusses the basics of Pd-NHC chemistry to understand the peculiarities of these catalysts and then gives a critical discussion on their application in C-C and C-N cross-coupling as well as carbopalladation reactions.

Palladium‐Catalyzed Carbonylation Reactions of Aryl Halides and Related Compounds

2009-05-08

Anne Brennführer , Helfried Neumann , Matthias Beller

Palladium-catalyzed carbonylation reactions of aromatic halides in the presence of various nucleophiles have undergone rapid development since the pioneering work of Heck and co-workers in 1974, such that nowadays a … Palladium-catalyzed carbonylation reactions of aromatic halides in the presence of various nucleophiles have undergone rapid development since the pioneering work of Heck and co-workers in 1974, such that nowadays a plethora of palladium catalysts are available for different carbonylative transformations. The carboxylic acid derivatives, aldehydes, and ketones prepared in this way are important intermediates in the manufacture of dyes, pharmaceuticals, agrochemicals, and other industrial products. In this Review, the recent academic developments in this area and the first industrial processes are summarized.

Recent Applications of Palladium‐Catalyzed Coupling Reactions in the Pharmaceutical, Agrochemical, and Fine Chemical Industries

2009-12-01

C. Torborg , Matthias Beller

Abstract Palladium‐catalyzed coupling reactions have become a central tool for the synthesis of biologically active compounds both in academia and industry. Most of these transformations make use of easily available … Abstract Palladium‐catalyzed coupling reactions have become a central tool for the synthesis of biologically active compounds both in academia and industry. Most of these transformations make use of easily available substrates and allow for a shorter and more selective preparation of substituted arenes and heteroarenes compared to non‐catalytic pathways. Notably, molecular‐defined palladium catalysts offer high chemoselectivity and broad functional group tolerance. Considering these advantages, it is not surprising that several palladium‐catalyzed coupling reactions have been implemented in the last decade into the industrial manufacture of pharmaceuticals and fine chemicals. In this review different examples from 2001–2008 are highlighted, which have been performed at least on a kilogram scale in the chemical and pharmaceutical industries.

Evolution of a Fourth Generation Catalyst for the Amination and Thioetherification of Aryl Halides

2008-08-06

John F. Hartwig

Many active pharmaceuticals, herbicides, conducting polymers, and components of organic light-emitting diodes contain arylamines. For many years, this class of compound was prepared via classical methods, such as nitration, reduction … Many active pharmaceuticals, herbicides, conducting polymers, and components of organic light-emitting diodes contain arylamines. For many years, this class of compound was prepared via classical methods, such as nitration, reduction and reductive alkylation, copper-mediated chemistry at high temperatures, addition to benzyne intermediates, or direct nucleophilic substitution on particularly electron-poor aromatic or heteroaromatic halides. However, during the past decade, palladium-catalyzed coupling reactions of amines with aryl halides have largely supplanted these earlier methods. Successive generations of catalysts have gradually improved the scope and efficiency of the palladium-catalyzed reaction. This Account describes the conceptual basis and utility of our latest, "fourth-generation" palladium catalyst for the coupling of amines and related reagents with aryl halides. In the past five years, we have developed these catalysts using the lessons learned from previous generations of catalysts developed in our group and in other laboratories. The ligands on the fourth-generation catalyst combine the chelating properties of the aromatic bisphosphines of the second-generation systems with the steric properties and strong electron donation of the hindered alkylphosphines of the third-generation systems. The currently most reactive catalyst in this class is generated from palladium and a sterically hindered version of the Josiphos family of ligands that possesses a ferrocenyl-1-ethyl backbone, a hindered di-tert-butylphosphino group, and a hindered dicyclohexylphosphino group. This system catalyzes the coupling of aryl chlorides, bromides, and iodides with primary amines, N−H imines, and hydrazones in high yield. The reaction has broad scope, high functional group tolerance, and nearly perfect selectivity for monoarylation. It also requires the lowest levels of palladium that have been used for C−N coupling. In addition, this latest catalyst has dramatically improved the coupling of thiols with haloarenes to form C−S bonds. Using ligands that lacked one or more of the structural elements of the most active catalyst, we examined the effects of individual structural elements of the Josiphos ligand on catalyst activity. This set of studies showed that each one of these elements contributes to the high reactivity and selectivity of the catalyst containing the hindered, bidentate Josiphos ligand. Finally, we examined the effect of electronic properties on the rates of reductive elimination to distinguish between the effect of the properties of the M−N σ-bond and the nitrogen electron pair. We have found that the effects of electronic properties on C−C and C−N bond-forming reductive elimination are similar. Because the amido ligands contain an electron pair, while the alkyl ligands do not, we have concluded that the major electronic effect is transmitted through the σ-bond.

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Selective carbon-carbon bond formation by cross-coupling of Grignard reagents with organic halides. Catalysis by nickel-phosphine complexes

1972-06-01

Kohei Tamao , Koji Sumitani , Makoto Kumada

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSelective carbon-carbon bond formation by cross-coupling of Grignard reagents with organic halides. Catalysis by nickel-phosphine complexesKohei Tamao, Koji Sumitani, and Makoto KumadaCite this: J. Am. Chem. Soc. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSelective carbon-carbon bond formation by cross-coupling of Grignard reagents with organic halides. Catalysis by nickel-phosphine complexesKohei Tamao, Koji Sumitani, and Makoto KumadaCite this: J. Am. Chem. Soc. 1972, 94, 12, 4374–4376Publication Date (Print):June 1, 1972Publication History Published online1 May 2002Published inissue 1 June 1972https://pubs.acs.org/doi/10.1021/ja00767a075https://doi.org/10.1021/ja00767a075research-articleACS PublicationsRequest reuse permissionsArticle Views16875Altmetric-Citations1098LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Palladium-Catalyzed Alkynylation

2003-04-15

Ei‐ichi Negishi , Luigi Anastasia

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPalladium-Catalyzed AlkynylationEi-ichi Negishi and Luigi AnastasiaView Author Information Herbert C. Brown Laboratories of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084 Cite this: Chem. Rev. 2003, 103, 5, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPalladium-Catalyzed AlkynylationEi-ichi Negishi and Luigi AnastasiaView Author Information Herbert C. Brown Laboratories of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084 Cite this: Chem. Rev. 2003, 103, 5, 1979–2018Publication Date (Web):April 15, 2003Publication History Received29 July 2002Published online15 April 2003Published inissue 1 May 2003https://pubs.acs.org/doi/10.1021/cr020377ihttps://doi.org/10.1021/cr020377iresearch-articleACS PublicationsCopyright © 2003 American Chemical SocietyRequest reuse permissionsArticle Views17447Altmetric-Citations1144LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Addition reactions,Cross coupling reaction,Electrophiles,Hydrocarbons,Reaction products Get e-Alerts

Palladium Nanoparticles on Graphite Oxide and Its Functionalized Graphene Derivatives as Highly Active Catalysts for the Suzuki−Miyaura Coupling Reaction

2009-05-25

Gil M. Scheuermann , Luigi Rumi , Peter Steurer +2 more

Pd2+-exchanged graphite oxide and chemically derived graphenes therefrom were employed as supports for Pd nanoparticles. The influence of catalyst preparation, carbon functionalization, and catalyst morphology on the catalytic activity in … Pd2+-exchanged graphite oxide and chemically derived graphenes therefrom were employed as supports for Pd nanoparticles. The influence of catalyst preparation, carbon functionalization, and catalyst morphology on the catalytic activity in the Suzuki−Miyaura coupling reactions was investigated. The catalysts were characterized by means of spectroscopy (FT-IR, solid-state 13C NMR, AAS, XPS), X-ray scattering (WAXS), surface area analysis (BET, methylene blue adsorption), and electron microscopy (TEM, ESEM). In contrast to the conventional Pd/C catalyst, graphite oxide and graphene-based catalysts gave much higher activities with turnover frequencies exceeding 39 000 h−1, accompanied by very low palladium leaching (<1 ppm).

Transition Metal Catalyzed Synthesis of Arylamines and Aryl Ethers from Aryl Halides and Triflates: Scope and Mechanism

1998-08-17

John F. Hartwig

Oxidative addition and reductive elimination are the central steps in new palladium-catalyzed chemistry that forms C–N and C–O bonds in arylamines and ethers. In the potential mechanism shown on the … Oxidative addition and reductive elimination are the central steps in new palladium-catalyzed chemistry that forms C–N and C–O bonds in arylamines and ethers. In the potential mechanism shown on the right the amine is formed by reductive elimination from a four-coordinate, 16-electron amido aryl complex. The use of a chelating ligand such as 1,1′-bis(diphenylphosphanyl)ferrocene (DPPF) reduces the occurrence of the competing β-hydrogen elimination. X=Br, I; R, R′=alkyl, aryl.

Aryl−Aryl Bond Formation by Transition-Metal-Catalyzed Direct Arylation

2007-01-01

Dino Alberico , Mark E. Scott , Mark Lautens

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAryl−Aryl Bond Formation by Transition-Metal-Catalyzed Direct ArylationDino Alberico, Mark E. Scott, and Mark LautensView Author Information Davenport Laboratories, Chemistry Department, University of Toronto, 80 St. George Street, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAryl−Aryl Bond Formation by Transition-Metal-Catalyzed Direct ArylationDino Alberico, Mark E. Scott, and Mark LautensView Author Information Davenport Laboratories, Chemistry Department, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada M5S 3H6 Cite this: Chem. Rev. 2007, 107, 1, 174–238Publication Date (Web):January 10, 2007Publication History Received6 July 2006Published online10 January 2007Published inissue 1 January 2007https://pubs.acs.org/doi/10.1021/cr0509760https://doi.org/10.1021/cr0509760research-articleACS PublicationsCopyright © 2007 American Chemical SocietyRequest reuse permissionsArticle Views36611Altmetric-Citations3415LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Anions,Aromatic compounds,Arylation,Catalysts,Organic reactions Get e-Alerts

N-Heterocyclic Carbenes: A New Concept in Organometallic Catalysis

2002-04-15

Wolfgang A. Herrmann

N-Heterocyclic carbenes have become universal ligands in organometallic and inorganic coordination chemistry. They not only bind to any transition metal, be it in low or high oxidation states, but also … N-Heterocyclic carbenes have become universal ligands in organometallic and inorganic coordination chemistry. They not only bind to any transition metal, be it in low or high oxidation states, but also to main group elements such as beryllium, sulfur, and iodine. Because of their specific coordination chemistry, N-heterocyclic carbenes both stabilize and activate metal centers in quite different key catalytic steps of organic syntheses, for example, C-H activation, C-C, C-H, C-O, and C-N bond formation. There is now ample evidence that in the new generation of organometallic catalysts the established ligand class of organophosphanes will be supplemented and, in part, replaced by N-heterocyclic carbenes. Over the past few years, this chemistry has been the field of vivid scientific competition, and yielded previously unexpected successes in key areas of homogeneous catalysis. From the work in numerous academic laboratories and in industry, a revolutionary turning point in oraganometallic catalysis is emerging.

Cross‐Coupling Reactions Of Organoboranes: An Easy Way To Construct CC Bonds (Nobel Lecture)

2011-05-25

Akira Suzuki

Tools for chemists: The Nobel Prize in Chemie 2010 was awarded for research on palladium-catalyzed cross-coupling in organic synthesis. Two of the Laureates, A. Suzuki and E. Negishi, report here … Tools for chemists: The Nobel Prize in Chemie 2010 was awarded for research on palladium-catalyzed cross-coupling in organic synthesis. Two of the Laureates, A. Suzuki and E. Negishi, report here first hand on the historical development and the current status of this research.

Dialkylbiaryl phosphines in Pd-catalyzed amination: a user's guide

2010-09-09

D. Surry , Stephen L. Buchwald

Dialkylbiaryl phosphines are a valuable class of ligand for Pd-catalyzed amination reactions and have been applied in a range of contexts. This perspective attempts to aid the reader in the … Dialkylbiaryl phosphines are a valuable class of ligand for Pd-catalyzed amination reactions and have been applied in a range of contexts. This perspective attempts to aid the reader in the selection of the best choice of reaction conditions and ligand of this class for the most commonly encountered and practically important substrate combinations.

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Palladium‐Catalyzed Cross‐Coupling Reactions in Total Synthesis

2005-06-30

K. C. Nicolaou , Paul G. Bulger , David Šarlah

In studying the evolution of organic chemistry and grasping its essence, one comes quickly to the conclusion that no other type of reaction plays as large a role in shaping … In studying the evolution of organic chemistry and grasping its essence, one comes quickly to the conclusion that no other type of reaction plays as large a role in shaping this domain of science than carbon-carbon bond-forming reactions. The Grignard, Diels-Alder, and Wittig reactions are but three prominent examples of such processes, and are among those which have undeniably exercised decisive roles in the last century in the emergence of chemical synthesis as we know it today. In the last quarter of the 20th century, a new family of carbon-carbon bond-forming reactions based on transition-metal catalysts evolved as powerful tools in synthesis. Among them, the palladium-catalyzed cross-coupling reactions are the most prominent. In this Review, highlights of a number of selected syntheses are discussed. The examples chosen demonstrate the enormous power of these processes in the art of total synthesis and underscore their future potential in chemical synthesis.

Carbon−Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium Catalysts

2006-12-21

Yin , Jürgen Liebscher

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCarbon−Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium CatalystsYin and Jürgen LiebscherView Author Information Institute für Chemie, Humboldt-Universität Berlin, Brook-Taylor-Strasse 2, D-12489 Berlin, Germany Cite this: Chem. Rev. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCarbon−Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium CatalystsYin and Jürgen LiebscherView Author Information Institute für Chemie, Humboldt-Universität Berlin, Brook-Taylor-Strasse 2, D-12489 Berlin, Germany Cite this: Chem. Rev. 2007, 107, 1, 133–173Publication Date (Web):December 21, 2006Publication History Received16 January 2006Published online21 December 2006Published inissue 1 January 2007https://pubs.acs.org/doi/10.1021/cr0505674https://doi.org/10.1021/cr0505674research-articleACS PublicationsCopyright © 2007 American Chemical SocietyRequest reuse permissionsArticle Views29168Altmetric-Citations1937LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Anions,Catalysts,Heck reaction,Palladium,Silica Get e-Alerts

On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis, A Critical Review

2006-04-01

Nam T. S. Phan , Matthew Van Der Sluys , Christopher Jones

A wide array of forms of palladium has been utilized as precatalysts for Heck and Suzuki coupling reactions over the last 15 years. Historically, nearly every form of palladium used … A wide array of forms of palladium has been utilized as precatalysts for Heck and Suzuki coupling reactions over the last 15 years. Historically, nearly every form of palladium used has been described as the active catalytic species. However, recent research has begun to shed light on the in situ transformations that many palladium precatalysts undergo during and before the catalytic reaction, and there are now many suggestions in the literature that narrow the scope of types of palladium that may be considered true “catalysts” in these coupling reactions. In this work, for each type of precatalyst, the recent literature is summarized and the type(s) of palladium that are proposed to be truly active are enumerated. All forms of palladium, including discrete soluble palladium complexes, solid-supported metal ligand complexes, supported palladium nano- and macroparticles, soluble palladium nanoparticles, soluble ligand-free palladium, and palladium-exchanged oxides are considered and reviewed here. A considerable focus is placed on solid precatalysts and on evidence for and against catalysis by solid surfaces vs. soluble species when starting with various precatalysts. The review closes with a critical overview of various control experiments or tests that have been used by authors to assess the homogeneity or heterogeneity of catalyst systems.

Recent advances in the cross-coupling reactions of organoboron derivatives with organic electrophiles, 1995–1998

1999-03-01

Akira Suzuki

Copper in cross-coupling reactions

2004-12-01

I. P. Beletskaya , Andrei V. Cheprakov

Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

2008-07-28

D. Surry , Stephen L. Buchwald

Palladium-catalyzed amination reactions of aryl halides have undergone rapid development in the last 12 years, largely driven by the implementation of new classes of ligands. Biaryl phosphanes have proven to … Palladium-catalyzed amination reactions of aryl halides have undergone rapid development in the last 12 years, largely driven by the implementation of new classes of ligands. Biaryl phosphanes have proven to provide especially active catalysts in this context. This Review discusses the application of these catalysts in C-N cross-coupling reactions in the synthesis of heterocycles and pharmaceuticals, in materials science, and in natural product synthesis.

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Selected Patented Cross-Coupling Reaction Technologies

2006-06-28

J.-P. Corbet , Gérard Mignani

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSelected Patented Cross-Coupling Reaction TechnologiesJean-Pierre Corbet and Gérard MignaniView Author Information Rhodia Recherches, Centre de Recherches et de Technologies de Lyon, 85 rue des Frères Perret, BP … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSelected Patented Cross-Coupling Reaction TechnologiesJean-Pierre Corbet and Gérard MignaniView Author Information Rhodia Recherches, Centre de Recherches et de Technologies de Lyon, 85 rue des Frères Perret, BP 62,69192 Saint-Fons Cedex, France Cite this: Chem. Rev. 2006, 106, 7, 2651–2710Publication Date (Web):June 28, 2006Publication History Received20 January 2006Published online28 June 2006Published inissue 1 July 2006https://doi.org/10.1021/cr0505268Copyright © 2006 American Chemical SocietyRequest reuse permissionsArticle Views20171Altmetric-Citations1602LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (2 MB) Get e-AlertscloseSUBJECTS:Catalysts,Coupling reactions,Ligands,Palladium Get e-Alerts

Metal‐Catalyzed Cross‐Coupling Reactions

1998-01-31

Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions

2016-09-30

Paula Ruiz‐Castillo , Stephen L. Buchwald

Pd-catalyzed cross-coupling reactions that form C–N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the … Pd-catalyzed cross-coupling reactions that form C–N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C–N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts.

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Pd Metal Catalysts for Cross-Couplings and Related Reactions in the 21st Century: A Critical Review

2018-02-20

Andrea Biffis , Paolo Centomo , Alessandro Del Zotto +1 more

Cross-couplings and related reactions are a class of highly efficient synthetic protocols that are generally promoted by molecular Pd species as catalysts. However, catalysts based on more or less highly … Cross-couplings and related reactions are a class of highly efficient synthetic protocols that are generally promoted by molecular Pd species as catalysts. However, catalysts based on more or less highly dispersed Pd metal have been also employed for this purpose, and their use, which was largely limited to the Heck reaction until the turn of the century, has been extended in recent years to most reactions of this class. This review provides a critical overview on these recent applications of Pd metal catalysts. Particular attention is devoted to the discussion of the mechanistic pathways that have been proposed to explain the catalytic role of Pd metal. Furthermore, the most outstanding Pd metal based catalytic systems that have emerged are illustrated, together with the development of novel approaches to boost the reactivity of Pd metal. A section summarizing the current industrial applications of Pd metal catalyzed reactions of this kind concludes the review.

Catalysts for Suzuki−Miyaura Coupling Processes: Scope and Studies of the Effect of Ligand Structure

2005-03-08

Timothy E. Barder , Shawn D. Walker , Joseph R. Martinelli +1 more

Suzuki−Miyaura coupling reactions of aryl and heteroaryl halides with aryl-, heteroaryl- and vinylboronic acids proceed in very good to excellent yield with the use of 2-(2',6'-dimethoxybiphenyl)dicyclohexylphosphine, SPhos (1). This ligand … Suzuki−Miyaura coupling reactions of aryl and heteroaryl halides with aryl-, heteroaryl- and vinylboronic acids proceed in very good to excellent yield with the use of 2-(2',6'-dimethoxybiphenyl)dicyclohexylphosphine, SPhos (1). This ligand confers unprecedented activity for these processes, allowing reactions to be performed at low catalyst levels, to prepare extremely hindered biaryls and to be carried out, in general, for reactions of aryl chlorides at room temperature. Additionally, structural studies of various 1·Pd complexes are presented along with computational data that help elucidate the efficacy that 1 imparts on Suzuki−Miyaura coupling processes. Moreover, a comparison of the reactions with 1 and with 2-(2',4',6'-triisopropylbiphenyl)diphenylphosphine (2) is presented that is informative in determining the relative importance of ligand bulk and electron-donating ability in the high activity of catalysts derived from ligands of this type. Further, when the aryl bromide becomes too hindered, an interesting C−H bond functionalization-cross-coupling sequence intervenes to provide product in high yield.

Rational Development of Practical Catalysts for Aromatic Carbon−Nitrogen Bond Formation

1998-10-21

John P. Wolfe , Seble Wagaw , Jean-François Marcoux +1 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRational Development of Practical Catalysts for Aromatic Carbon−Nitrogen Bond FormationJohn P. Wolfe, Seble Wagaw, Jean-François Marcoux, and Stephen L. BuchwaldView Author Information Department of Chemistry, Massachusetts Institute … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRational Development of Practical Catalysts for Aromatic Carbon−Nitrogen Bond FormationJohn P. Wolfe, Seble Wagaw, Jean-François Marcoux, and Stephen L. BuchwaldView Author Information Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 Cite this: Acc. Chem. Res. 1998, 31, 12, 805–818Publication Date (Web):October 21, 1998Publication History Received26 March 1998Published online21 October 1998Published inissue 1 December 1998https://pubs.acs.org/doi/10.1021/ar9600650https://doi.org/10.1021/ar9600650research-articleACS PublicationsCopyright © 1998 American Chemical SocietyRequest reuse permissionsArticle Views16157Altmetric-Citations1652LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Amines,Anions,Aromatic compounds,Ligands,Organic reactions Get e-Alerts

Modern Synthetic Methods for Copper‐Mediated C(aryl)O, C(aryl)N, and C(aryl)S Bond Formation

2004-02-18

Steven V. Ley , Andrew W. Thomas

In the Review “Modern Synthetic Methods for Copper-Mediated C(aryl)O, C(aryl)N, and C(aryl)S Bond Formation” by S. V. Ley and A. W. Thomas1, the “Avendano-Modified Ullmann Condensation Reaction” (Section 1.1, Equation … In the Review “Modern Synthetic Methods for Copper-Mediated C(aryl)O, C(aryl)N, and C(aryl)S Bond Formation” by S. V. Ley and A. W. Thomas1, the “Avendano-Modified Ullmann Condensation Reaction” (Section 1.1, Equation 11) should be correctly termed the “Barton Plumbane-Modified Ullmann Condensation Reaction”. Furthermore, the following important references are missing: D. H. R. Barton, N. Yadav-Bhatnagar, J.-P. Finet, J. Khamsi, Tetrahedron Lett. 1987, 28, 3111–3114; D. H. R. Barton, D. M. X. Donnely, J.-P. Finet, P. J. Guiry, Tetrahedron Lett. 1989, 30, 1377–1380; D. H. R. Barton, D. M. X. Donnely, J.-P. Finet, P. J. Guiry, J. Chem. Soc. Perkin Trans. 1 1991, 2095–2102.

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Handbook of Organopalladium Chemistry for Organic Synthesis

2002-07-26

Ei‐ichi Negishi

PREFACE. CONTRIBUTORS. INTRODUCTION AND BACKGROUND. Historical Background of Organopalladium Chemistry Fundamental Properties of Palladium and Patterns of the Reactions of Palladium and Its Complexes. PALLADIUM COMPOUNDS: STOICHIOMETRIC PREPARATION, IN SITU … PREFACE. CONTRIBUTORS. INTRODUCTION AND BACKGROUND. Historical Background of Organopalladium Chemistry Fundamental Properties of Palladium and Patterns of the Reactions of Palladium and Its Complexes. PALLADIUM COMPOUNDS: STOICHIOMETRIC PREPARATION, IN SITU GENERATION, AND SOME PHYSICAL AND CHEMICAL PROPERTIES. Background for Part II. Pd(0) and Pd(II) Compounds Without Carbon-Palladium Bonds. Organopalladium Compounds Containing Pd(0) and Pd(II). Palladium Complexes Containing Pd(I), Pd(III), or Pd(IV). PALLADIUM-CATALYZED REACTIONS INVOLVING REDUCTIVE ELIMINATION. Background for Part III. Palladium-Catalyzed Carbon-Carbon Cross-Coupling. Palladium-Catalyzed Carbon-Hydrogen and Carbon- Heteroatom Coupling. PALLADIUM-CATALYZED REACTIONS INVOLVING CARBOPALLADATION. Background for Part IV. The Heck Reaction (Alkene Substitution via Carbopalladation- Dehydropalladation) and Related Carbopalladation Reactions. Palladium-Catalyzed Tandem and Cascade Carbopalladation of Alkynes and 1,1-Disubstituted Alkenes. Allylpalladation and Related Reactions of Alkenes, Alkynes, Dienes, and Other -Compounds. Alkynyl Substitution via Alkynylpalladation-Reductive Elimination. Arene Substitution via Addition-Elimination. Carbopalladation of Allenes. Synthesis of Natural Products via Carbopalladation. Cyclopropanation and Other Reactions of Palladium-Carbene (and Carbyne) Complexes. Carbopalladation via Palladacyclopropanes and Palladacyclopropenes. Palladium-Catalyzed Carbozincation. PALLADIUM-CATALYZED REACTIONS INVOLVING NUCLEOPHILIC ATTACK ON LIGANDS. Background for Part V. Palladium-Catalyzed Nucleophilic Substitution Involving Allylpalladium, Propargylpalladium, and Related Derivatives. Palladium-Catalyzed Reactions Involving Nucleophilic Attack on -Ligands of Palladium-Alkene, Palladium-Alkyne, and Related Derivatives. PALLADIUM-CATALYZED CARBONYLATION AND OTHER RELATED REACTIONS INVOLVING MIGRATORY INSERTION. Background for Part VI. Migratory Insertion Reactions of Alkyl-, Aryl-, Alkenyl-, and Alkynylpalladium Derivatives Involving Carbon Monoxide and Related Derivatives. Migratory Insertion Reactions of Allyl, Propargyl, and Allenylpalladium Derivatives Involving Carbon Monoxide and Related Derivatives. Acylpalladation and Related Addition Reactions. Other Reactions of Acylpalladium Derivatives. Synthesis of Natural Products via Palladium-Catalyzed Carbonylation. Palladium-Catalyzed Carbonylative Oxidation. Synthesis of Oligomeric and Polymeric Materials via Palladium-Catalyzed Successive Migratory Insertion of Isonitriles. CATALYTIC HYDROGENATION AND OTHER PALLADIUM-CATALYZED REACTIONS VIA HYDROPALLADATION, METALLOPALLADATION, AND OTHER RELATED SYN ADDITION REACTIONS WITHOUT CARBON-CARBON BOND FORMATION OR CLEAVAGE. Background for Part VII. Palladium-Catalyzed Hydrogenation. Palladium-Catalyzed Isomerization of Alkenes, Alkynes, and Related Compounds without Skeletal Rearrangements. Palladium-Catalyzed Hydrometallation. Metallopalladation. Palladium-Catalyzed Syn-Addition Reactions of X-Pd Bonds (X = Group 15, 16, and 17 Elements). PALLADIUM-CATALYZED OXIDATION REACTIONS THAT HAVE NOT BEEN DISCUSSED IN EARLIER PARTS. Background for Part VIII. Oxidation via Reductive Elimination of Pd(II) and Pd(IV) Complexes. Palladium-Catalyzed or -Promoted Oxidation via 1,2- or 1,4-Elimination. Other Miscellaneous Palladium-Catalyzed or -Promoted Oxidation Reactions. REARRANGEMENT AND OTHER MISCELLANEOUS REACTIONS CATALYZED BY PALLADIUM. Background for Part IX. Rearrangement Reactions Catalyzed by Palladium. TECHNOLOGICAL DEVELOPMENTS IN ORGANOPALLADIUM CHEMISTRY. Aqueous Palladium Catalysis. Palladium Catalysts Immobilized on Polymeric Supports. Organopalladium Reactions in Combinatorial Chemistry. REFERENCES. General Guidelines on References Pertaining to Palladium and Organopalladium Chemistry. Books (Monographs). Reviews and Accounts (as of September 1999). SUBJECT INDEX.

Nickel-Catalyzed Enantioconvergent C(sp3)–C(sp3) Cross-Coupling between α-Iodogermanes and Alkylzinc Reagents

2025-06-25

Emilio Gabriel Andreas Acuña Bolomey , Martin Oestreich | Synthesis

We report a nickel-catalyzed enantioconvergent C(sp³)–C(sp³) cross-coupling between α-iodogermanes and alkylzinc reagents to access α-chiral alkylgermanes. This transformation, a strategy previously established for silicon-based electrophiles extends to germanium, enabling the … We report a nickel-catalyzed enantioconvergent C(sp³)–C(sp³) cross-coupling between α-iodogermanes and alkylzinc reagents to access α-chiral alkylgermanes. This transformation, a strategy previously established for silicon-based electrophiles extends to germanium, enabling the enantioselective formation of α-chiral germanes from simple, unactivated alkyl chains. While yields and enantioselectivities remain moderate, the reaction outcome was finely tuned through the design and evaluation of a library of over 30 ligands, including more than a dozen novel scaffolds. Notably, two distinct NiBr₂∙PyBox complexes allowed for access to products of opposite absolute configuration, and preformed nickel complexes were required to reach synthetically useful conversions. These findings highlight the challenges of asymmetric catalysis with heavier main-group elements and provide a platform for the future design of ligands tailored to organogermanium chemistry.

Divergent Synthesis of Heterotricyclic Compounds from γ-Alkynyl-1,3-diketones via Base-Mediated Tandem Annulations

2025-06-24

Ming‐Yang Chang , Yizhen Lin , Fang-Yi Jen +3 more | Organic Letters

This paper presents a novel base-mediated strategy for the divergent synthesis of oxygen- and nitrogen-containing heterotricyclic compounds, furo[3,2-c]chromene and furo[3,2-c]quinolone, from γ-alkynyl 1,3-diketones without the use of transition metals. These … This paper presents a novel base-mediated strategy for the divergent synthesis of oxygen- and nitrogen-containing heterotricyclic compounds, furo[3,2-c]chromene and furo[3,2-c]quinolone, from γ-alkynyl 1,3-diketones without the use of transition metals. These one-pot tandem reaction methodologies demonstrate remarkable versatility, enabling base-mediated O-attack via 5-exo-dig or C-attack intramolecular cyclization onto the alkyne, leading to the formation of furo[3,2-c]chromene or xanthone products. Additionally, sequential reactions involving regioselective condensation followed by tandem annulation afford furo[3,2-c]quinolone. These approaches leverage precisely controlled reaction conditions to direct selective annulation pathways, facilitating the construction of diverse heterocyclic frameworks with significant pharmaceutical potential.

Rutile TiO2 Confined Atomic Palladium Species Boosts C−C Coupling Efficiency in Sonogashira Coupling Reactions

2025-06-24

Zhijun Li , Hongxue Liu , Albert Pang +7 more | Advanced Functional Materials

Abstract Developing high‐performance Pd‐based catalysts with ultra‐low Pd loading is essential but challenging for the multi‐step Sonogashira coupling reactions. Structure–function relationships for single atom catalysts (SACs) are highly dependent on … Abstract Developing high‐performance Pd‐based catalysts with ultra‐low Pd loading is essential but challenging for the multi‐step Sonogashira coupling reactions. Structure–function relationships for single atom catalysts (SACs) are highly dependent on the coordination environments of active sites on appropriate supports. Herein, a facile strategy consisting of crystal phase engineering and thermal atomization to access a Pd‐based SAC with 0.35 wt% Pd loading (Pd 1 /TiO 2‐ x ) is reported. The resulting material consists of spatially isolated Pd atoms decorated on rutile TiO 2 (a support that is frequently overlooked in catalyst design). The use of this Pd catalyst in the Sonogashira C−C coupling of iodobenzene and phenylacetylene to diphenylacetylene achieves distinguished catalytic efficacy, rendering a high yield of 98% and a turnover frequency (TOF) of 23 809 h −1 , which is comparable to similar state‐of‐the‐art catalysts. Mechanistic investigations disclose that this strategy promotes interfacial electron transfer between the metal and support, endowing a unique electronic structure and ensuring electronic metal–support coupling effects in Pd 1 /TiO 2‐ x . This significantly affects the adsorption/activation of reactants and the desorption of intermediates/products, thereby strongly boosting the coupling efficiency. These findings highlight the great importance of catalyst design for multi‐step coupling reactions.

PdO‐CuO Nanoparticles Supported on Fe2O3 Nanoplate as Highly Effective Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reaction

2025-06-24

Juanjuan Yin , Meining Chen , Ying Wang +3 more | ChemNanoMat

The palladium‐catalyzed Suzuki–Miyaura coupling reaction (SMC) serves as a pivotal method for constructing carbon–carbon bonds in organic synthesis. In this study, a bimetallic Pd‐Cu/Fe 2 O 3 nanoplate catalyst are … The palladium‐catalyzed Suzuki–Miyaura coupling reaction (SMC) serves as a pivotal method for constructing carbon–carbon bonds in organic synthesis. In this study, a bimetallic Pd‐Cu/Fe 2 O 3 nanoplate catalyst are rationally designed and synthesized through a sequential impregnation strategy. The phase composition, morphological features, and surface electronic states of the catalyst are systematically characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), and H 2 ‐temperature‐programmed reduction (TPR). Remarkably, this heterogeneous nanocatalyst exhibits outstanding catalytic activity for SMC reactions under mild temperature of 40 °C, achieving 99% product yield within 15 min in the absence of toxic solvents or phase‐transfer agents. The superior catalytic performance is mainly attributed to the coexistence of Pd 2+ and Pd δ+ (2 < δ < 4) on the support surface and the synergistic effect between PdO and CuO nanoparticles. Furthermore, the catalyst demonstrates excellent recyclability, retaining 90% of its initial activity after five consecutive cycles. This study provides a viable strategy for developing energy‐efficient heterogeneous catalysts through bimetallic synergy.

Deciphering Tryptophan Oxygenation: Key Modulators of 2‐Oxindole Formation in MarE

2025-06-24

Romie C. Nguyen , Inchul Shin , Aimin Liu | Angewandte Chemie

MarE, a heme‐dependent aromatic oxygenase with a histidyl axial ligated, catalyzes the monooxygention of β‐methyl‐L‐tryptophan, to form a 2‐oxindole scaffold central to maremycin biosynthesis. Although structurally similar to tryptophan 2,3‐dioxygenase … MarE, a heme‐dependent aromatic oxygenase with a histidyl axial ligated, catalyzes the monooxygention of β‐methyl‐L‐tryptophan, to form a 2‐oxindole scaffold central to maremycin biosynthesis. Although structurally similar to tryptophan 2,3‐dioxygenase (TDO), which initiates L‐tryptophan catabolism via dioxygenation, MarE exhibits distinct reactivity modulated by ascorbate. While ascorbate has no effect on TDO, it promotes selective monooxygenation by MarE. In its absence, MarE favors dioxygenation and formation of furoindoline‐like products, revealing a latent catalytic versatility. Active‐site loop sequences differ between the two enzymes, SLGGR in MarE versus GTGGS in TDO, prompting loop‐swapping experiments to probe structure‐function relationships. Substituting GTGGS in TDO with MarE‐like sequences (GTGGA or SLGGS) shifted reactivity toward monooxygenation and formation of C3‐hydroxylated, non‐oxindole products that underwent further cyclization into three‐ring structures. Conversely, replacing SLGGR in MarE with GTGGS in enhanced C2,C3‐dioxygenation nearly 4‐fold. These results underscore the active‐site loop as a key determinant of oxidation outcome in addition to ascorbate. demonstrating the critical role of the active site loop in oxidation site preference. By revealing the true catalytic identity of MarE and delineating the roles of small‐molecule effectors and loop architecture, this study advances mechanistic understanding and predictive capabilities within the oxygenase superfamily.

Synthesis of Primary Arylamines by Electrochemical Nickel-Catalyzed Amination of Aryl Halides with NH3

2025-06-23

| Synfacts

Directing-Group-Enabled Palladium-Catalyzed Reverse Regioselective Dicarbofunctionalization of Acrylamides

2025-06-23

| Synfacts

Tin-Free Palladium-Catalyzed Coupling of Secondary Amines with Aryl Bromides

2025-06-23

| Synfacts

Ni/Ti Dual Catalyzed Cross-Electrophile Coupling between Unactivated Alkyl Chlorides and Aryl Halides

2025-06-23

Devi Oniani , Xiaofan Jia , Emily L. Mane +7 more | ACS Catalysis

Stereoselective Synthesis of Tetrasubstituted Alkenes from 1,2-Diketones via Oxyphosphonium Salts-Engaged Suzuki–Miyaura Coupling

2025-06-20

Bin Zhang , Jinyan Wan , Chuan Zhu +1 more | Organic Letters

We report an efficient and stereoselective synthesis of tetrasubstituted alkenes through palladium-catalyzed Suzuki-Miyaura coupling of arylboronate esters with O-alkenyl oxyphosphonium salts. These electrophilic partners are prepared from 1,2-diketones via the … We report an efficient and stereoselective synthesis of tetrasubstituted alkenes through palladium-catalyzed Suzuki-Miyaura coupling of arylboronate esters with O-alkenyl oxyphosphonium salts. These electrophilic partners are prepared from 1,2-diketones via the Kukhtin-Ramirez reaction followed by O-methylation. The protocol achieves high yields and excellent Z/E selectivity using Pd(OAc)2 with commercially available phosphine ligands, wherein ligand selection enables stereochemical control. Preliminary mechanistic studies suggest that the isomerization of the critical alkenyl-palladium intermediate dictates the product configuration. By integrating Kukhtin-Ramirez chemistry with cross-coupling technology, this methodology establishes a streamlined platform for converting 1,2-diketones into synthetically challenging tetrasubstituted alkenes.

Palladium Nanoparticles Dispersed in Alginate Beads as an Efficient, Eco‐friendly, and Sustainable Heteregeneous Catalyst: Testing in Carbon‐Sulfur and Carbon‐Carbon Cross‐Coupling Reactions

2025-06-19

K. Ramesh , Katla Rakhi , Daniel Rapachi +4 more | Asian Journal of Organic Chemistry

Abstract The development of sustainable and efficient catalysts featuring palladium nanoparticles (Pd NPs) is highly sought after. In this context, sodium alginate, a natural polymer, presents a promising eco‐friendly support … Abstract The development of sustainable and efficient catalysts featuring palladium nanoparticles (Pd NPs) is highly sought after. In this context, sodium alginate, a natural polymer, presents a promising eco‐friendly support material for Pd NPs. Thus, this study reports the synthesis of a solid material which consists of sodium alginate beads containing uniformly dispersed Pd NPs (named palladium/copper alginate beads, Pd/CuAB). This material was fully characterized using analytical techniques of ultraviolet–visible spectrophotometry (UV–vis), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), transmission electron microscopy (TEM), and inductively coupled plasma optical emission spectrometry (ICP‐OES). It is evaluated as a catalyst in both carbon‐sulfur (C‐S) and carbon‐carbon (C‐C) cross‐coupling reactions. The catalytic system used for the C‐S coupling demonstrated high efficiency and broad compatibility with substrates containing different substituent groups. For the Suzuki–Miyaura C‐C coupling, the catalytic system showed excellent performance with aryl iodides as substrates. However, for aryl bromides, the results suggest that further optimizations are needed to achieve satisfactory reaction yields. Therefore, the Pd/CuAB catalyst showed surprising performance in C‐S coupling and may be among the best described in the literature. In addition, the stability in air, ease of handling and use of sustainably sourced catalytic support are noteworthy points of the Pd/CuAB solid. Based on these results, this study contributes to the advancement of the state‐of‐the‐art of palladium catalysts employing sustainable catalytic supports.

Designing and immobilizing gold nanoparticles over a lignosulfonate/starch composite for Suzuki-Miyaura coupling reactions, and investigation of its anti-pancreatic and anti-hepatitis cancer effects

2025-06-19

Huigang Zhang , Aixiang Liu , Attalla F. El‐kott +6 more | Arabian Journal of Chemistry

Nickel-catalyzed amination of aryl halides: An exogenous ligand-free approach to primary arylamines using TMSN3

2025-06-19

Jiawei Huang , Xiaoman Li , Zhigang Lei +2 more | Journal of Catalysis

IPr* and Its Analog for Arene-Induced Precatalyst Activation and Stabilization in Ni-Catalyzed Kumada–Tamao–Corriu Coupling of Unactivated Aryl Halides

2025-06-17

Kouki Matsubara , Y. YAMADA , AMBROSE M. TOKUSHIGE +3 more | Organometallics

Direct Access of Heteroaryl Difunctional Monomers for Arene-Enriched Polysiloxane Synthesis

2025-06-17

Shaila A. Shetu , Jihyeon Nam , Jongwook Choi +3 more | Organic Letters

Step- and atom-economical catalytic C-H silylations were developed to prepare heteroaryl alkoxysilane monomers for silicone materials. The silylations are operable in the presence of 1-3 mol % of a well-defined … Step- and atom-economical catalytic C-H silylations were developed to prepare heteroaryl alkoxysilane monomers for silicone materials. The silylations are operable in the presence of 1-3 mol % of a well-defined Rh complex to afford the desired aryl monomers in up to 95% yield. The preformed complexes are able to suppress silane redistribution side reactions so as to improve overall efficiency of less reactive HSiMe(OEt)2. The resulting monomers will broaden the scope of aryl substituents that is currently limited to only phenyl groups, so that various polysiloxanes bearing nonphenyl aryl substituents can be readily prepared with modulating physical and chemical properties.

Palladium/Copper Co-catalyzed ipso-Alkynylation and ortho-Alkylation of Aryl Halides

2025-06-17

Yijun Shi , Xuejing Liu , Chengwei Liu | Synthesis

A palladium/copper co-catalyzed ipso-alkynylation and ortho-alkylation has been reported. Aromatic halides, including aryl iodides and aryl bromides, can be used as substrates in this reaction. Furthermore, alkyl halides, including alkyl … A palladium/copper co-catalyzed ipso-alkynylation and ortho-alkylation has been reported. Aromatic halides, including aryl iodides and aryl bromides, can be used as substrates in this reaction. Furthermore, alkyl halides, including alkyl iodides, alkyl bromides, and alkyl chlorides, can be used as alkylation reagents for this approach. Broad substrate scope and excellent functional group tolerance of this platform has been demonstrated in the highly selective ipso-alkynylation and ortho-alkylation. The desired reactions were operated under mild and operationally-practical conditions providing a powerful approach for functionalizing of aryl halides.

Green Approach for Copper‐Free Pd‐catalyzed Sonogashira Cross‐Coupling using Saponin‐Based Micellar Catalysis in Water at Ambient Temperature

2025-06-16

Vinothkumar Vinayagam , Subir Kumar Sadhukhan , M. Saravana Kumar +2 more | European Journal of Organic Chemistry

A micellar catalysis that is derived from commercially available saponin for copper‐free, Pd‐catalyzed Sonogashira cross‐coupling under mild reaction conditions has been developed. Using this green and sustainable method, a broad … A micellar catalysis that is derived from commercially available saponin for copper‐free, Pd‐catalyzed Sonogashira cross‐coupling under mild reaction conditions has been developed. Using this green and sustainable method, a broad range of aryl/heteroaryl and alkyl terminal alkynes were cross‐coupled with aryl/heteroaryl halides at ambient temperature in an aqueous medium. The commercially available, inexpensive, and plant‐based natural saponin served as a surfactant for a micellar system that effectively enabled C(sp2)‐C(sp) cross‐coupling with a wide range of substrates. The attractive features of this protocol are the use of water as a reaction medium, the in‐situ generation of the micellar‐catalysis system from biodegradable natural saponins, good functional group tolerance, scalability of the products, and notably the ability to retain the catalyst activity by recycling the aqueous reaction medium.

Highly Active Catalyst for Suzuki–Miyaura Coupling to Form Sterically Demanding Biaryls: Electronic Control of Pd through the Secondary Interaction Using a Buchwald-Type Ligand Bearing a Fluorinated Aryl Ring

2025-06-16

Toshinobu Korenaga , Honoka Obata , Shigeki Moriya +1 more | Organic Letters

To accelerate reductive elimination in Suzuki-Miyaura coupling (SMC) through secondary interactions with a Buchwald-type ligand, a heptafluorotolyl group was introduced into the ligand's structure, guided by DFT calculations. The resulting … To accelerate reductive elimination in Suzuki-Miyaura coupling (SMC) through secondary interactions with a Buchwald-type ligand, a heptafluorotolyl group was introduced into the ligand's structure, guided by DFT calculations. The resulting ligand, HFTPhos, was effective for SMC, enabling the formation of sterically demanding biaryls. The catalyst loading could be reduced to as low as 0.025 mol % for tetra-ortho-substituted biaryls and 0.001 mol % for tri-ortho-substituted biaryls.

Mechanism of Nickel-Catalyzed Dual C–O Bond Activation in the Deoxygenation of Ethers via Reductive Cross-Coupling Reaction: A DFT Study

2025-06-16

Felipe Zauith Assad , Ataualpa Albert Carmo Braga | Organometallics

Confined Catalysis Involving a Palladium Complex and a Self-Assembled Capsule for the Dimerization of Vinyl Arenes and the Formation of Indane and Tribenzo–Pentaphene Derivatives

2025-06-12

Maxime Steinmetz , David Sémeril | Catalysts

The [PdCl2(cod)] complex was encapsulated inside a self-assembled hexameric capsule obtained via a reaction of 2,8,14,20-tetra-undecyl-resorcin[4]arene and water. The formation of an inclusion complex was deduced from a combination of … The [PdCl2(cod)] complex was encapsulated inside a self-assembled hexameric capsule obtained via a reaction of 2,8,14,20-tetra-undecyl-resorcin[4]arene and water. The formation of an inclusion complex was deduced from a combination of spectral measurements (UV-visible, 1H NMR and DOSY spectroscopies). The latter proved effective in the dimerization of styrene derivatives under mild conditions, with a catalyst loading of 0.5 mol% at 60 °C. Electronically enriched vinyl arenes underwent cyclization of the catalytic products, leading to the quasi-quantitative formation of indanes from 4-tert-butylstyrene and 9-vinylanthracene. In the instance of 9-vinylanthracene, the rearrangement product is tribenzo–pentaphene, which is formed in 50% of conversions.

Synthesis of Biaryls via Pd‐Catalyzed Cross‐Coupling Reaction between Arene Carboxylic Acids and Aryl Thianthrenium Trifluoromethanesulfonates

2025-06-03

Pierre Boulay , Malang Konte , Jacques Lalevée +1 more | European Journal of Organic Chemistry

A simple aryl–aryl bond‐forming reaction via palladium‐catalyzed cross‐coupling between cheap and easily accessible arene carboxylic acids and aryl thianthrenium trifluoromethanesulfonates is described. It turns out that the use of PdCl … A simple aryl–aryl bond‐forming reaction via palladium‐catalyzed cross‐coupling between cheap and easily accessible arene carboxylic acids and aryl thianthrenium trifluoromethanesulfonates is described. It turns out that the use of PdCl 2 in the presence of Ag 2 CO 3 in DMSO at 120 °C is the most efficient system for performing this reaction. Various biaryls, bearing electron‐donating or electron‐withdrawing groups, including sterically hindered biaryls are successfully obtained. The amount of waste generated during this cross‐coupling is minimized since thianthrene obtained as a by‐product can be easily recovered and reused after reaction.

Suzuki–Miyaura Coupling of Pinacolboronic Esters Catalyzed by a Well-Defined Palladium N-Heterocyclic Carbene (NHC) Catalyst

2025-06-03

Aleksei A. Logvinov , Geert Rombouts , Matthieu Jouffroy +1 more | ACS Medicinal Chemistry Letters

We report a versatile synthetic method for coupling heteroaryl chlorides and bromides with (hetero)-aryl pinacolboronic esters of pharmaceutical interest at low catalyst loading of a well-defined palladium-NHC catalyst providing products … We report a versatile synthetic method for coupling heteroaryl chlorides and bromides with (hetero)-aryl pinacolboronic esters of pharmaceutical interest at low catalyst loading of a well-defined palladium-NHC catalyst providing products in good to high isolated yield and purity in short reaction time. The method displays remarkably broad applicability with both 5- and 6-membered heterocycles.

In-situ formation of nanoparticles from a sulfur-ligated palladacycle: Catalytic performance in Suzuki-Miyaura and Sonogashira reactions

2025-06-01

Jolly Kaushal , Sain Singh , Pramod Kumar | Inorganic Chemistry Communications

[Ni(PnBu3)2Cl2] as an economical precatalyst for the Suzuki-Miyaura cross coupling reaction of aryl sulfonate esters and halides

2025-06-01

E. Constant , Armaan Grewal , Eric C. Keske | Tetrahedron Letters

Efficient Chemoselective Sequential Pd-Catalyzed Suzuki Coupling of Highly Functionalized Iodoaryl Triflates

2025-06-01

Till Schreiner , Philipp Reitinger , Maria Degli Innocenti +2 more | Tetrahedron