Organolithiums: Selectivity for Synthesis

Organolithiums: Selectivity for Synthesis

1st Edition - July 1, 2002

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  • Author: J Clayden
  • eBook ISBN: 9780080538167

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This volume, number 23 in the "Tetrahedron Organic Chemistry" series, presents organolithium chemistry from the perspective of a synthetic organic chemist, drawing from the synthetic literature to present a unified overview of how organolithiums can be used to make molecules. The development of methods for the regioselective synthesis of organolithiums has replaced their image of indiscriminate high reactivity with one of controllable and subtle selectivity. Organolithium chemistry has a central role in the selective construction of C-C bonds in both simple and complex molecules, and for example has arguably overtaken aromatic electrophilic substitution as the most powerful method for regioselective functionalisation of aromatic rings. The twin themes of reactivity and selectivity run through the book, which reviews the ways by which organolithiums may be formed and the ways in which they react. Topics include advances in directed metallation, reductive lithiation and organolithium cyclisation reactions, along with a discussion of organolithium stereochemistry and the role played by ligands such as (-)-sparteine.

Table of Contents

    • Foreword
    • Acknowledgements
      • Publisher Summary
    • Abbreviations
      • Publisher Summary
    • Chapter 1: Introduction
      • 1.1 Scope and Overview
      • 1.2 Organolithiums in solution
    • Chapter 2: Regioselective Synthesis of Organolithiums by Deprotonation
      • 2.1 General points
      • 2.2 Lithiation α to heteroatoms
      • 2.3 Ortholithiation
      • 2.4 Lateral Lithiation
      • 2.5 Remote lithiation, and β-lithiation of non-aromatic compounds
      • 2.6 Superbases435
      • 2.7 Cooperation, competition and regioselectivity
    • Chapter 3: Regioselective Synthesis of Organolithiums by X-Li Exchange
      • 3.1 Halogen-lithium exchange
      • 3.2 Tin-lithium exchange
      • 3.3 Chalcogen-lithium exchange
      • 3.4 Phosphorus-lithium exchange
    • Chapter 4: Regioselective Synthesis of Organolithiums by C–X Reduction
      • 4.1 Reductive lithiation of alkyl and aryl halides
      • 4.2 Reductive lithiation of C–O bonds9
      • 4.3 Reductive lithiation of C–N bonds
      • 4.4 Reductive lithiation of C–S bonds
      • 4.5 Reductive lithiation of C–C bonds and π-bonds
    • Chapter 5: Stereoselective and Stereospecific Synthesis of Organolithiums
      • 5.1 Configurational Stability of Organolithiums
      • 5.2 Stereospecific synthesis of organolithiums by X-Li exchange
      • 5.3 Diastereoselective deprotonation
      • 5.4 Enantioselective Deprotonation
    • Chapter 6: Stereoselective and Stereospecific Substitution Reactions of Organolithiums
      • 6.1 Stereospecific reactions of organolithium compounds
      • 6.2 Stereoselective substitution in the presence of chiral ligands
    • Chapter 7: Regio- and Stereoselective Addition Reactions of Organolithiums
      • 7.1 Intermolecular addition to π bonds: Carbolithiation
      • 7.2 Intramolecular addition and substitution reactions: anionic cyclisation
    • Chapter 8: Organolithium Rearrangements
      • 8.1 Shapiro Reaction13
      • 8.2 Brook Rearrangements1921
      • 8.3 [1,2]-Wittig Rearrangements6466
      • 8.4 [2,3]-Wittig Rearrangements9092
    • Chapter 9: Organolithiums in Synthesis
      • 9.1 Ochratoxin: ortholithiation and anionic ortho-Fries rearrangement1
      • 9.2 Corydalic acid methyl ester: lateral lithiation2
      • 9.3 Fredericamycin A: ortho, lateral and α-lithiation3
      • 9.4 (±)-Atpenin B: lithiation of an aromatic heterocycle4
      • 9.5 Flurbiprofen: metallation with LiCKOR superbases5
      • 9.6 California Red Scale Pheromone: α- and reductive lithiation6
      • 9.7 C1-C9 of the Bryostatins: diastereoselective bromine-lithium exchange7
      • 9.8 (S)-1-Methyldodecyl acetate, a Drosophila pheromone: (−)-sparteine assisted enantioselective lithiation8
      • 9.9 (−)-Paroxetine: (−)-sparteine-promoted asymmetric lithiation and substitution9
    • Index
      • Publisher Summary

Product details

  • No. of pages: 400
  • Language: English
  • Copyright: © Pergamon 2002
  • Published: July 1, 2002
  • Imprint: Pergamon
  • eBook ISBN: 9780080538167

About the Author

J Clayden

Affiliations and Expertise

Department of Chemistry University of Manchester Manchester UK

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