Organolithiums : selectivity for synthesis /

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Bibliographic Details
Author / Creator:Clayden, Jonathan.
Edition:1st ed.
Imprint:Amsterdam ; Boston : Pergamon, 2002.
Description:xvi, 383 p. : ill. ; 24 cm.
Language:English
Series:Tetrahedron organic chemistry series ; v. 23
Subject:
Format: Print Book
URL for this record:http://pi.lib.uchicago.edu/1001/cat/bib/4843751
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ISBN:008043262X
0080432611 (pbk.)
Notes:Includes bibliographical references and index.
Table of Contents:
  • Foreword
  • Acknowledgements
  • Abbreviations
  • Chapter 1. Introduction
  • 1.1. Scope and overview
  • 1.2. Organolithiums in solution
  • References
  • Chapter 2. Regioselective Synthesis of Organolithiums by Deprotonation
  • 2.1. General points
  • 2.2. Lithiation [alpha] to heteroatoms
  • 2.2.1. Lithiation [alpha] to oxygen
  • 2.2.2. Lithiation [alpha] to nitrogen
  • 2.2.2.1. Amides
  • 2.2.2.2. Benzotriazoles and other 5-membered heterocycles
  • 2.2.2.3. Formamidines
  • 2.2.2.4. Nitrosoamines
  • 2.2.2.5. Imines
  • 2.2.2.6. Isocyanides
  • 2.2.2.7. Lithiation of trigonal C-H [alpha] to nitrogen
  • 2.2.2.8. N-oxides and amine-boron complexes
  • 2.2.3. Lithiation [alpha] to sulfur
  • 2.2.4. Lithiation [alpha] to silicon
  • 2.2.5. Lithiation at unfunctionalised allylic positions
  • 2.3. Ortholithiation
  • 2.3.1. Introduction: mechanism
  • 2.3.2. Classes of directing group
  • 2.3.2.1. N+O class
  • 2.3.2.1.1. Secondary and tertiary amides
  • 2.3.2.1.2. [alpha]-Amino alkoxides
  • 2.3.2.1.3. Oxazolines
  • 2.3.2.1.4. O-Carbamates
  • 2.3.2.1.5. Anilides and N-aryl carbamates
  • 2.3.2.2. S+O class
  • 2.3.2.3. N class
  • 2.3.2.3.1. Aminomethyl groups
  • 2.3.2.3.2. Anilines and isocyanides
  • 2.3.2.3.3. Imines, nitriles, hydrazones and nitrogen heterocycles
  • 2.3.2.4. O class
  • 2.3.2.4.1. Ethers and alkoxides
  • 2.3.2.4.2. Ketones, esters and carboxylates
  • 2.3.2.5. X class
  • 2.3.3. Ortholithiation of aromatic heterocycles
  • 2.3.3.1. Electron-deficient heterocycles
  • 2.3.3.2. Electron-rich heterocycles
  • 2.3.4. Lithiation of metal-arene complexes
  • 2.3.4.1. Chromium-arene complexes
  • 2.3.4.2. Ferrocenes
  • 2.4. Lateral lithiation
  • 2.4.1. Mechanism and regioselectivity
  • 2.4.2. Classes of directing group
  • 2.4.2.1. Secondary and tertiary amides
  • 2.4.2.2. Nitriles
  • 2.4.2.3. Oxazolines, imidazolines and tetrazoles
  • 2.4.2.4. Carboxylates
  • 2.4.2.5. Carboxylic esters
  • 2.4.2.6. Ketones
  • 2.4.2.7. Aldehydes protected as [alpha]-amino alkoxides
  • 2.4.2.8. Alcohols and phenols (cresols) and their derivatives
  • 2.4.2.9. Sulfur-based functional groups
  • 2.4.2.10. Aniline and aminoalkylbenzene derivatives
  • 2.4.2.11. Halogens
  • 2.4.2.12. Lateral lithiation of heterocycles
  • 2.5. Remote lithiation, and [beta]-lithiation of non-aromatic compounds
  • 2.6. Superbases
  • 2.7. Cooperation, competition and regioselectivity
  • References
  • Chapter 3. Regioselective Synthesis of Organolithiums by X-Li Exchange
  • 3.1. Halogen-lithium exchange
  • 3.1.1. Reactivity
  • 3.1.2. Mechanism
  • 3.1.3. Synthesis of aryllithiums
  • 3.1.4. Synthesis of heteroaryllithiums
  • 3.1.5. Synthesis of vinyllithiums
  • 3.1.6. Synthesis of alkyllithiums
  • 3.1.7. Diastereoselective halogen-lithium exchange
  • 3.2. Tin-lithium exchange
  • 3.3. Chalcogen-lithium exchange
  • 3.3.1. Selenium-lithium exchange
  • 3.3.2. Tellurium-lithium exchange
  • 3.3.3. Sulfur-lithium exchange
  • 3.4. Phosphorus-lithium exchange
  • References
  • Chapter 4. Regioselective Synthesis of Organolithiums by C-X Reduction
  • 4.1. Reductive lithiation of alkyl and aryl halides
  • 4.1.1. Reductive lithiation with lithium metal
  • 4.1.2. Reductive lithiation promoted by arenes
  • 4.2. Reductive lithiation of C-O bonds
  • 4.3. Reductive lithiation of C-N bonds
  • 4.4. Reductive lithiation of C-S bonds
  • 4.4.1. Reduction of sulfides
  • 4.4.2. Reduction of sulfones
  • 4.5. Reductive lithiation of C-C bonds and [pi]-bonds
  • References
  • Chapter 5. Stereoselective and Stereospecific Synthesis of Organolithiums
  • 5.1. Configurational stability of organolithiums
  • 5.1.1. Determining configurational stability
  • 5.1.2. Unfunctionalised organolithiums
  • 5.1.2.1. Secondary organolithiums
  • 5.1.2.2. Primary organolithiums
  • 5.1.2.3. Solvent effects
  • 5.1.3. Cyclopropyllithiums
  • 5.1.4. Organolithiums [alpha] to oxygen
  • 5.1.4.1. Simple acyclic [alpha]-alkoxy organolithiums
  • 5.1.4.2. Cyclic [alpha]-alkoxy organolithiums
  • 5.1.4.3. Oxiranyllithiums
  • 5.1.4.4. Allylic and benzylic [alpha]-alkoxy organolithiums
  • 5.1.5. Organolithiums [alpha] to nitrogen
  • 5.1.5.1. Cyclic [alpha]-amino organolithiums: 3-membered rings
  • 5.1.5.2. Pyrrolidinyllithiums and piperidinyllithiums: 5- and 6-membered rings
  • 5.1.5.3. Lithiated formamidines
  • 5.1.5.4. Acyclic [alpha]-amino organolithiums
  • 5.1.5.5. Benzylic and allylic [alpha]-amino organolithiums
  • 5.1.5.6. Crystallographic and theoretical data
  • 5.1.6. Organolithiums [alpha] to halogens
  • 5.1.7. Organolithiums [alpha] to sulfur
  • 5.1.7.1. Lithiated sulfides
  • 5.1.7.2. Lithiated thiocarbamates
  • 5.1.7.3. Lithiated sulfones
  • 5.1.7.4. Mechanism of racemisation
  • 5.1.8. Organolithiums [alpha] to selenium
  • 5.1.9. Organolithiums [alpha] to phosphorus
  • 5.1.10. Organolithiums [alpha] to silicon
  • 5.1.11. Benzyllithiums
  • 5.1.11.1. Secondary benzyllithiums
  • 5.1.11.2. Tertiary benzyllithiums
  • 5.1.12. Vinyllithiums
  • 5.1.13. Summary
  • 5.2. Stereospecific synthesis of organolithiums by X-Li exchange
  • 5.2.1. Tin-lithium exchange
  • 5.2.1.1. Vinylstannanes
  • 5.2.1.2. [alpha]-Heterosubstituted stannanes
  • 5.2.1.3. Non-heterosubstituted stannanes
  • 5.2.2. Halogen-lithium exchange
  • 5.2.3. Selenium-lithium exchange
  • 5.2.4. Sulfur-lithium exchange
  • 5.2.5. Other metal-lithium exchanges
  • 5.2.6. Stereospecific deprotonation
  • 5.3. Diastereoselective deprotonation
  • 5.3.1. Diastereoselective lateral lithiation
  • 5.3.2. Diastereoselective ortholithiation
  • 5.4. Enantioselective deprotonation
  • References
  • Chapter 6. Stereospecific and Stereoselective Substitution Reactions of Organolithiums
  • 6.1. Stereospecific reactions of organolithium compounds
  • 6.1.1. Introduction
  • 6.1.2. Vinyllithiums
  • 6.1.3. Non-stabilised alkyllithiums
  • 6.1.3.1. The general rule: retention (S[subscript E]2ret)
  • 6.1.3.2. The exception - alkylation of lithiated N-alkyl pyrrolidines and piperidines: inversion (S[subscript E]2inv)
  • 6.1.3.3. Rearrangements ([1,2] and [2,3], except Brook rearrangements) of unstabilised organolithiums: inversion (S[subscript E]2inv)
  • 6.1.4. Stabilised alkyllithiums: retention (S[subscript E]2ret) or inversion (S[subscript E]2inv)?
  • 6.1.4.1. Benzyllithiums
  • 6.1.4.2. Allyllithiums
  • 6.1.4.3. Rearrangements of stabilised organolithiums
  • 6.2. Stereoselective substitution in the presence of chiral ligands
  • 6.2.1. Introduction: Mechanisms
  • 6.2.2. Chiral ligands
  • 6.2.3. Enantioselective deprotonation
  • 6.2.4. Enantioselective substitution
  • 6.2.5. Configurational stability, stereospecificity, and dynamic resolutions
  • 6.2.6. Dynamic thermodynamic resolution
  • 6.2.7. Dynamic kinetic resolution
  • 6.2.8. Summary: mechanisms of asymmetric functionalisation with (-)-sparteine
  • References
  • Chapter 7. Regio- and Stereoselective Addition Reactions of Organolithiums
  • 7.1. Intermolecular addition to [pi] bonds: Carbolithiation
  • 7.1.1. Carbolithiation of simple alkenes
  • 7.1.2. Carbolithiation of conjugated alkenes and alkynes
  • 7.1.3. Carbolithiation of functionalised alkenes
  • 7.1.4. Enantioselective carbolithiation
  • 7.2. Intramolecular addition and substitution reactions: anionic cyclisation
  • 7.2.1. Anionic cyclisations onto carbonyl compounds and derivatives
  • 7.2.1.1. Cyclisations of aryllithiums - Parham cyclisations
  • 7.2.1.2. Cyclisations of alkenyllithiums
  • 7.2.1.3. Cyclisations of alkyllithiums
  • 7.2.1.4. Cyclisations of alkynyllithiums
  • 7.2.2. Anionic cyclisations onto epoxides
  • 7.2.3. Anionic cyclisations onto alkyl halides and similar compounds
  • 7.2.4. Anionic cyclisations onto alkenes and alkynes
  • 7.2.4.1. Cyclisation onto activated alkenes
  • 7.2.4.2. Cyclisation onto unactivated alkenes
  • 7.2.4.2.1. Cyclopentanes
  • 7.2.4.2.2. Cascade reactions
  • 7.2.4.2.3. Tetrahydrofurans
  • 7.2.4.2.4. Pyrrolidines
  • 7.2.4.2.5. Tetrahydrothiophenes
  • 7.2.4.2.6. Stereoselectivity and mechanism
  • 7.2.4.3. Anionic cyclisation onto allenes
  • 7.2.4.4. Anionic cyclisation onto alkynes
  • 7.2.4.6. Anionic cyclisation onto aromatic rings
  • References
  • Chapter 8. Organolithium Rearrangements
  • 8.1. Shapiro Reaction
  • 8.2. Brook Rearrangements
  • 8.2.1. [1,2]-Brook Rearrangements
  • 8.2.2. [1,3]-Brook Rearrangements
  • 8.2.3. [1,4]-Brook Rearrangements
  • 8.2.4. [1,4]-Retro-Brook rearrangements
  • 8.3. [1,2]-Wittig Rearrangements
  • 8.3.1. Mechanism and scope
  • 8.3.2. Stereospecificity
  • 8.3.3. [1,2]-Wittig rearrangements in synthesis
  • 8.4. [2,3]-Wittig Rearrangements
  • 8.4.1. Regioselectivity
  • 8.4.2. Diastereoselectivity
  • 8.4.2.1. Double bond geometry
  • 8.4.2.2. Syn/anti relative stereochemistry
  • 8.4.3. Stereospecificity and enantioselectivity
  • 8.4.3.1. Stereospecific rearrangements of chiral allyl ethers
  • 8.4.3.2. Stereoselective rearrangements with chiral auxiliaries
  • 8.4.3.3. Stereospecific rearrangements of chiral organolithiums
  • 8.4.4. [2,3]-Aza-Wittig rearrangements
  • References
  • Chapter 9. Organolithiums in Synthesis
  • 9.1. Ochratoxin: ortholithiation and anionic Fries rearrangement
  • 9.2. Corydalic acid methyl ester: lateral lithiation
  • 9.3. Fredericamycin A: ortho, lateral and [alpha]-lithiation
  • 9.4. ([plus or minus])-Atpenin B: metallation of an aromatic heterocycle
  • 9.5. Flurbiprofen: metallation with LiCKOR superbases
  • 9.6. California Red Scale Pheromone: [alpha]- and reductive lithiation
  • 9.7. C1-C9 of the Bryostatins: diastereoselective bromine-lithium exchange
  • 9.8. (S)-1-Methyldodecyl acetate, a Drosophila pheromone: (-)-sparteine assisted enantioselective lithiation
  • 9.9. (-)-Paroxetine: (-)-sparteine-promoted asymmetric lithiation and substitution
  • References
  • Index