Homologation reactions : reagents, applications, and mechanisms / / edited by Vittorio Pace

• Pubblicazione: Weinheim, Germany : , : WILEY-VCH GmbH, , [2023]; ©2023
• Descrizione fisica: 1 online resource (952 pages)
• Disciplina: 410.5
• Soggetto topico: Organic compounds - Synthesis
• Persona (resp. second.): PaceVittorio
• Nota di bibliografia: Includes bibliographical references and index.
• Nota di contenuto: Cover -- Volume1 -- Title Page -- Copyright -- Contents -- Foreword -- Preface -- Acknowledgments -- Chapter 1 Diazo‐Mediated Homologation Reactions -- 1.1 Introduction -- 1.2 Diazo Reagents for Homologations -- 1.2.1 Diazoalkanes -- 1.2.1.1 Diazomethane -- 1.2.1.2 Other Diazoalkanes -- 1.2.1.3 Fluorinated Diazoalkanes -- 1.2.1.4 Aryl Diazomethanes -- 1.2.2 Trimethylsilyl Diazomethane and Lithium Congener -- 1.2.3 α‐Diazocarbonyl Compounds -- 1.2.3.1 Diazotization of Amines -- 1.2.3.2 Dehydrogenation of Hydrazones, Tosylhydrazones, and Oximes -- 1.2.3.3 Acylation of Diazoalkanes -- 1.2.3.4 Diazo‐Transfer Reaction -- 1.2.3.5 Electrophilic Substitution and Cross‐Coupling in Diazo Compound -- 1.2.3.6 Substituent Modification -- 1.2.4 Seyferth-Gilbert and Bestmann-Ohira Reagents -- 1.3 Homologation of Aldehydes and Ketones -- 1.3.1 Buchner-Curtius-Schlotterbeck Reaction -- 1.3.2 Roskamp Reaction -- 1.3.3 Tiffeneau-Demjanov Rearrangement -- 1.3.4 Seyferth-Gilbert Homologation -- 1.3.5 Colvin Rearrangement -- 1.4 Homologation of Carboxylic Acids -- 1.4.1 Homologation of α‐Amino Acids -- 1.4.1.1 N‐Protecting Group -- 1.4.1.2 Activation of Carboxylic Acids -- 1.4.1.3 β‐Peptide Synthesis -- 1.5 Miscellaneous Homologations -- 1.6 Summary and Outlook -- References -- Chapter 2 Lithium Carbenoids in Homologation Chemistry -- 2.1 Introduction -- 2.2 Lithium Carbenoids Generation -- 2.2.1 Metal-Halide Exchange -- 2.2.2 Metal-Proton Exchange -- 2.2.3 Metal-Sulfinyl Exchange -- 2.2.4 Lithium-Tin Exchange -- 2.3 Transmetallation -- 2.4 Carbenoids Configurational Stability -- 2.5 Electrophilic Partners of Lithium Carbenoids -- 2.5.1 Carbonyl Adducts -- 2.5.2 Carboxylic Acid Chlorides -- 2.5.3 Homologation of Benzyl Halides -- 2.5.4 Imines -- 2.5.5 Esters and Weinreb Amides -- 2.5.6 Homologation of Heterocumulenes -- 2.5.7 Homologation of Heteroatom Electrophiles. ; 2.6 Fluoromethylating Carbenoids -- 2.7 Fluorinated Lithium Carbenoids Acting as Electrophiles -- 2.8 Homologation of Heteroatom‐Centered Cycles with Lithium Carbenoids -- 2.9 Recent Applications of Lithium Carbenoids in the Homologation of Boron Electrophiles -- 2.10 Conclusions and Outlook -- References -- Chapter 3 Streamlining C1 Homologation Reactions Using Continuous Flow Technology: Focus on Diazomethane and Methyllithium Chemistry -- 3.1 Introduction: Flow Technology for On‐site Generation and Use of Hazardous and Highly Reactive Homologation Reagents -- 3.2 Methods and Tools for the Flow Synthesis and C1 Homologation Reaction of Diazomethane -- 3.2.1 Introduction -- 3.2.2 Continuous Flow Generation of Diazomethane -- 3.2.3 Homologation Reactions Using Diazomethane under Flow Conditions -- 3.2.4 Flow Synthesis and Reaction of Trimethylsilyldiazomethane -- 3.3 Generation and Use of α‐Halomethyllithium Carbenoids under Continuous Flow Conditions -- 3.3.1 Introduction -- 3.3.2 Bromo‐Containing Lithium Halomethyl Carbenoids -- 3.3.3 Chloro‐Containing Lithium Halomethyl Carbenoids -- 3.3.4 Fluoro‐Containing Lithium Halomethyl Carbenoids -- 3.3.4.1 Other Examples of Continuous Flow C1 Homologations Using Fluoromethyl Units -- 3.3.5 C1 Homologation Mediated by Halomethylmagnesium Intermediate -- 3.4 Conclusions and Outlook -- References -- Chapter 4 Magnesium Carbenoids in Homologation Chemistry -- 4.1 Introduction -- 4.2 Synthesis of α‐Chloro‐Substituted Sulfoxides as Magnesium Carbenoid Precursors -- 4.3 Reactivity of Magnesium Carbenoids -- 4.4 Homologation of Carbonyl Compounds via β‐Oxido Carbenoid Rearrangement -- 4.5 Homologation of Carbonyl Compounds via the Nucleophilic Substitution of Enolates with Magnesium Carbenoids -- 4.6 Ring Expansion of Lithium Phenolates and Naphtholates. ; 4.7 Synthesis of One‐Carbon Homologated Alkynes from Carbonyl Compounds -- 4.8 Homologation of Grignard Reagents -- References -- Chapter 5 Homologation Reactions Based on Zinc Carbenoids and Related Reagents -- 5.1 Introduction -- 5.2 Organozinc Species for Methylene Homologation -- 5.3 Zinc Carbenoid‐Mediated Homologation Reactions -- 5.3.1 Zercher Homologation Reactions -- 5.3.1.1 Simple Zercher Homologation Reactions of β‐Keto Carbonyl and Related Compounds -- 5.3.1.2 Tandem Reactions Initiated by Zercher Homologations -- 5.3.2 Homologative Cross‐Coupling Reactions with Organometallic Reagents -- 5.3.2.1 Overview -- 5.3.2.2 Homologative Cross‐Coupling Reactions with Copper Organometallics -- 5.3.2.3 Homologative Cross‐Coupling Reactions with Vinylcopper Reagents -- 5.3.2.4 Homologative Cross‐Coupling Reactions with Alkynyl‐ and Allenylcopper Reagents -- 5.3.2.5 Homologative Cross‐Coupling Reactions with Alkyl Copper or Lithium Reagents -- 5.4 Zinc‐Mediated Homologation Reactions Using CH2(ZnI)2 -- 5.4.1 Homologation Reactions Initiated by the Addition of CH2(ZnI)2 to Carbonyl Compounds -- 5.4.1.1 Overview -- 5.4.1.2 CH2(ZnI)2‐Mediated Homologative Coupling Reactions of Enones -- 5.4.1.3 CH2(ZnI)2‐Mediated Homologative Coupling Reactions of α‐Substituted Ketones -- 5.4.1.4 CH2(ZnI)2‐Mediated Homologative Coupling Reactions of Isocyanates -- 5.4.1.5 CH2(ZnI)2‐Mediated Homologative Acylation Reactions -- 5.4.2 Metal‐Catalyzed Homologative Cross‐Electrophile Coupling Using CH2(ZnI)2 -- 5.4.2.1 Overview -- 5.4.2.2 CH2(ZnI)2‐Mediated Homologative Acylation of Electrophiles -- 5.4.2.3 Metal‐Catalyzed Homologative Cross‐Electrophile Coupling Using CH2(ZnI)2 -- 5.5 Summary -- References -- Chapter 6 Homologation Reactions via Carbene Transfer Reaction‐Mediated Rearrangement Reactions -- 6.1 Introduction. ; 6.2 [1,2]‐Sigmatropic Rearrangement of Onium Ylides -- 6.2.1 Homologation Reactions of Group VI Ylides via Carbene Transfer Reaction -- 6.2.2 Iodonium Ylides -- 6.3 Carbene Insertion Reaction into X X Bonds -- 6.3.1 Insertion Reactions into E E Bonds of Group VI Elements -- 6.4 Ring Expansion Reactions of Oxygen and Sulfur Heterocycles via Homologation Reaction -- 6.5 Conclusions and Perspective -- References -- Chapter 7 Oxenoids as Homologation Partners -- 7.1 General Introduction -- 7.2 Introduction of Oxenoids -- 7.2.1 General Consideration, Structure, and Electrophilic Nature of Oxenoids -- 7.3 Reactions of Oxenoids with Nucleophiles: Homologation Reactions -- 7.4 Conclusions and Outlook -- Acknowledgments -- References -- Chapter 8 Sulfur Ylides as C1 Homologating Reagents -- 8.1 Introduction -- 8.2 Historical Background -- 8.3 Reactivity of Sulfur Ylides as C1 Homologating Reagents -- 8.3.1 Sulfur Ylides in Epoxidation Reactions and Applications in Synthesis -- 8.3.2 Sulfur Ylides as Reagents for the Synthesis of Alkenes -- 8.3.3 Sulfur Ylides as Reagents for the Synthesis of Aldehydes -- 8.3.4 Sulfur Ylides in Aziridination Reactions -- 8.3.5 Sulfur Ylides as Reagents in Miscellaneous Reactions -- 8.4 Reactivity of Sulfoxonium Ylides as C1 Homologating Reagents -- 8.4.1 Sulfoxonium Ylides in Epoxidation Reactions and Applications in Synthesis -- 8.4.2 Sulfoxonium Ylides in Aziridination Reactions -- 8.4.3 Sulfoxonium Ylides in Cyclopropanation Reactions -- 8.4.4 Sulfoxonium Ylides as Reagents for the Synthesis of Indoles -- 8.4.5 Sulfoxonium Ylides as Reagents for the Synthesis of Carbonates -- 8.4.6 Sulfoxonium Ylides as Reagents for Iterative C1 Homologations Leading to Boranes -- 8.4.7 Sulfoxonium Ylides as Reagents in Miscellaneous Reactions -- 8.5 Conclusions -- References. ; Chapter 9 Modern Homologation Reactions of Sulfoxonium Ylides via C-H Activation -- 9.1 Introduction -- 9.2 Rh‐Catalyzed C-H Homologation Reactions -- 9.2.1 Simple Homologations -- 9.2.2 [4+2] Annulations -- 9.2.3 [3+2] Annulations -- 9.2.4 [5+2] Annulations -- 9.2.5 [3+3] Annulations -- 9.2.6 [4+1] Annulations -- 9.3 Ir‐Catalyzed C-H Homologation Reactions -- 9.3.1 Simple Homologations -- 9.3.2 [3+2] Annulations -- 9.3.3 [4+2] Annulations -- 9.4 Ru‐Catalyzed C-H Homologation Reactions -- 9.4.1 Simple Homologations -- 9.4.2 [4+2] Annulations -- 9.4.3 [3+2] Annulations -- 9.4.4 [3+3] Annulations -- 9.4.5 [4+1] Annulations -- 9.4.6 [5+1] Annulations -- 9.5 Co‐Catalyzed C-H Homologation Reactions -- 9.5.1 Simple Homologations -- 9.5.2 [4+2] Annulations -- 9.6 Miscellaneous Homologation Reactions -- 9.7 Summary -- Acknowledgments -- References -- Chapter 10 Phosphorus Reagents for Two‐, Three‐, and Four‐Carbon Homologation of Carbonyl Compounds to Functionalized Olefins -- 10.1 Introduction -- 10.2 Two‐Carbon Homologation -- 10.2.1 Classical Methods for Two‐Carbon Homologation -- 10.2.2 Horner-Wadsworth-Emmons and Related Reagents -- 10.2.3 Still-Gennari and Ando Reagents -- 10.2.4 Stabilized Wittig Reagents -- 10.2.5 Non‐stabilized Acetal‐Protected Wittig Reagents -- 10.2.6 DualPhos -- 10.2.7 Aldehyde to Methyl Ketone Homologation and Vinyl Ether Synthesis -- 10.2.8 Semi‐stabilized and Stabilized Reagents in Aqueous Mild Base and Organocatalytic Homologation -- 10.2.9 Applications in Asymmetric Organocatalysis and Total Synthesis -- 10.3 Three‐Carbon and Four‐Carbon Homologation Reagents -- 10.4 Summary and Outlook -- References -- Chapter 11 Homologation Tactics with Diborylmethane via α‐Boryl Carbanions -- 11.1 Introduction -- 11.2 Reactivity with α‐Borylmethide Carbanions. ; 11.2.1 Palladium Borylmethide Salts Homologate Aryl, Allyl, and Benzyl Electrophiles.
• Titolo autorizzato: Homologation reactions
• ISBN: 3-527-83021-9; 3-527-83022-7; 3-527-83023-5
• Formato: Materiale a stampa
• Livello bibliografico: Monografia
• Lingua di pubblicazione: Inglese
• Record Nr.: 9910728381903321
• Lo trovi qui: Univ. Federico II