Organolithiums : selectivity for synthesis /
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Author / Creator: | Clayden, Jonathan. |
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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 |
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