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| Foreword | |
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| Acknowledgements | |
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| Abbreviations | |
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| Introduction | |
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| Scope and overview | |
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| Organolithiums in solution | |
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| References | |
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| Regioselective Synthesis of Organolithiums by Deprotonation | |
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| General points | |
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| Lithiation [alpha] to heteroatoms | |
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| Lithiation [alpha] to oxygen | |
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| Lithiation [alpha] to nitrogen | |
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| Amides | |
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| Benzotriazoles and other 5-membered heterocycles | |
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| Formamidines | |
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| Nitrosoamines | |
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| Imines | |
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| Isocyanides | |
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| Lithiation of trigonal C-H [alpha] to nitrogen | |
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| N-oxides and amine-boron complexes | |
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| Lithiation [alpha] to sulfur | |
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| Lithiation [alpha] to silicon | |
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| Lithiation at unfunctionalised allylic positions | |
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| Ortholithiation | |
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| Introduction: mechanism | |
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| Classes of directing group | |
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| N+O class | |
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| Secondary and tertiary amides | |
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| [alpha]-Amino alkoxides | |
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| Oxazolines | |
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| O-Carbamates | |
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| Anilides and N-aryl carbamates | |
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| S+O class | |
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| N class | |
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| Aminomethyl groups | |
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| Anilines and isocyanides | |
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| Imines, nitriles, hydrazones and nitrogen heterocycles | |
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| O class | |
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| Ethers and alkoxides | |
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| Ketones, esters and carboxylates | |
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| X class | |
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| Ortholithiation of aromatic heterocycles | |
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| Electron-deficient heterocycles | |
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| Electron-rich heterocycles | |
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| Lithiation of metal-arene complexes | |
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| Chromium-arene complexes | |
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| Ferrocenes | |
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| Lateral lithiation | |
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| Mechanism and regioselectivity | |
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| Classes of directing group | |
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| Secondary and tertiary amides | |
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| Nitriles | |
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| Oxazolines, imidazolines and tetrazoles | |
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| Carboxylates | |
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| Carboxylic esters | |
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| Ketones | |
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| Aldehydes protected as [alpha]-amino alkoxides | |
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| Alcohols and phenols (cresols) and their derivatives | |
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| Sulfur-based functional groups | |
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| Aniline and aminoalkylbenzene derivatives | |
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| Halogens | |
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| Lateral lithiation of heterocycles | |
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| Remote lithiation, and [beta]-lithiation of non-aromatic compounds | |
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| Superbases | |
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| Cooperation, competition and regioselectivity | |
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| References | |
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| Regioselective Synthesis of Organolithiums by X-Li Exchange | |
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| Halogen-lithium exchange | |
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| Reactivity | |
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| Mechanism | |
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| Synthesis of aryllithiums | |
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| Synthesis of heteroaryllithiums | |
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| Synthesis of vinyllithiums | |
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| Synthesis of alkyllithiums | |
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| Diastereoselective halogen-lithium exchange | |
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| Tin-lithium exchange | |
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| Chalcogen-lithium exchange | |
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| Selenium-lithium exchange | |
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| Tellurium-lithium exchange | |
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| Sulfur-lithium exchange | |
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| Phosphorus-lithium exchange | |
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| References | |
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| Regioselective Synthesis of Organolithiums by C-X Reduction | |
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| Reductive lithiation of alkyl and aryl halides | |
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| Reductive lithiation with lithium metal | |
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| Reductive lithiation promoted by arenes | |
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| Reductive lithiation of C-O bonds | |
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| Reductive lithiation of C-N bonds | |
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| Reductive lithiation of C-S bonds | |
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| Reduction of sulfides | |
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| Reduction of sulfones | |
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| Reductive lithiation of C-C bonds and [pi]-bonds | |
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| References | |
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| Stereoselective and Stereospecific Synthesis of Organolithiums | |
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| Configurational stability of organolithiums | |
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| Determining configurational stability | |
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| Unfunctionalised organolithiums | |
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| Secondary organolithiums | |
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| Primary organolithiums | |
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| Solvent effects | |
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| Cyclopropyllithiums | |
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| Organolithiums [alpha] to oxygen | |
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| Simple acyclic [alpha]-alkoxy organolithiums | |
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| Cyclic [alpha]-alkoxy organolithiums | |
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| Oxiranyllithiums | |
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| Allylic and benzylic [alpha]-alkoxy organolithiums | |
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| Organolithiums [alpha] to nitrogen | |
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| Cyclic [alpha]-amino organolithiums: 3-membered rings | |
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| Pyrrolidinyllithiums and piperidinyllithiums: 5- and 6-membered rings | |
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| Lithiated formamidines | |
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| Acyclic [alpha]-amino organolithiums | |
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| Benzylic and allylic [alpha]-amino organolithiums | |
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| Crystallographic and theoretical data | |
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| Organolithiums [alpha] to halogens | |
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| Organolithiums [alpha] to sulfur | |
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| Lithiated sulfides | |
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| Lithiated thiocarbamates | |
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| Lithiated sulfones | |
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| Mechanism of racemisation | |
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| Organolithiums [alpha] to selenium | |
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| Organolithiums [alpha] to phosphorus | |
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| Organolithiums [alpha] to silicon | |
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| Benzyllithiums | |
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| Secondary benzyllithiums | |
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| Tertiary benzyllithiums | |
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| Vinyllithiums | |
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| Summary | |
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| Stereospecific synthesis of organolithiums by X-Li exchange | |
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| Tin-lithium exchange | |
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| Vinylstannanes | |
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| [alpha]-Heterosubstituted stannanes | |
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| Non-heterosubstituted stannanes | |
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| Halogen-lithium exchange | |
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| Selenium-lithium exchange | |
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| Sulfur-lithium exchange | |
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| Other metal-lithium exchanges | |
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| Stereospecific deprotonation | |
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| Diastereoselective deprotonation | |
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| Diastereoselective lateral lithiation | |
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| Diastereoselective ortholithiation | |
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| Enantioselective deprotonation | |
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| References | |
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| Stereospecific and Stereoselective Substitution Reactions of Organolithiums | |
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| Stereospecific reactions of organolithium compounds | |
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| Introduction | |
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| Vinyllithiums | |
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| Non-stabilised alkyllithiums | |
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| The general rule: retention (S[subscript E]2ret) | |
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| The exception - alkylation of lithiated N-alkyl pyrrolidines and piperidines: inversion (S[subscript E]2inv) | |
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| Rearrangements ([1,2] and [2,3], except Brook rearrangements) of unstabilised organolithiums: inversion (S[subscript E]2inv) | |
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| Stabilised alkyllithiums: retention (S[subscript E]2ret) or inversion (S[subscript E]2inv)? | |
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| Benzyllithiums | |
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| Allyllithiums | |
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| Rearrangements of stabilised organolithiums | |
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| Stereoselective substitution in the presence of chiral ligands | |
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| Introduction: Mechanisms | |
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| Chiral ligands | |
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| Enantioselective deprotonation | |
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| Enantioselective substitution | |
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| Configurational stability, stereospecificity, and dynamic resolutions | |
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| Dynamic thermodynamic resolution | |
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| Dynamic kinetic resolution | |
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| Summary: mechanisms of asymmetric functionalisation with (-)-sparteine | |
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| References | |
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| Regio- and Stereoselective Addition Reactions of Organolithiums | |
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| Intermolecular addition to [pi] bonds: Carbolithiation | |
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| Carbolithiation of simple alkenes | |
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| Carbolithiation of conjugated alkenes and alkynes | |
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| Carbolithiation of functionalised alkenes | |
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| Enantioselective carbolithiation | |
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| Intramolecular addition and substitution reactions: anionic cyclisation | |
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| Anionic cyclisations onto carbonyl compounds and derivatives | |
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| Cyclisations of aryllithiums - Parham cyclisations | |
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| Cyclisations of alkenyllithiums | |
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| Cyclisations of alkyllithiums | |
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| Cyclisations of alkynyllithiums | |
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| Anionic cyclisations onto epoxides | |
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| Anionic cyclisations onto alkyl halides and similar compounds | |
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| Anionic cyclisations onto alkenes and alkynes | |
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| Cyclisation onto activated alkenes | |
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| Cyclisation onto unactivated alkenes | |
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| Cyclopentanes | |
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| Cascade reactions | |
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| Tetrahydrofurans | |
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| Pyrrolidines | |
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| Tetrahydrothiophenes | |
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| Stereoselectivity and mechanism | |
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| Anionic cyclisation onto allenes | |
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| Anionic cyclisation onto alkynes | |
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| Anionic cyclisation onto aromatic rings | |
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| References | |
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| Organolithium Rearrangements | |
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| Shapiro Reaction | |
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| Brook Rearrangements | |
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| [1,2]-Brook Rearrangements | |
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| [1,3]-Brook Rearrangements | |
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| [1,4]-Brook Rearrangements | |
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| [1,4]-Retro-Brook rearrangements | |
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| [1,2]-Wittig Rearrangements | |
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| Mechanism and scope | |
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| Stereospecificity | |
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| [1,2]-Wittig rearrangements in synthesis | |
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| [2,3]-Wittig Rearrangements | |
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| Regioselectivity | |
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| Diastereoselectivity | |
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| Double bond geometry | |
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| Syn/anti relative stereochemistry | |
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| Stereospecificity and enantioselectivity | |
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| Stereospecific rearrangements of chiral allyl ethers | |
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| Stereoselective rearrangements with chiral auxiliaries | |
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| Stereospecific rearrangements of chiral organolithiums | |
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| [2,3]-Aza-Wittig rearrangements | |
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| References | |
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| Organolithiums in Synthesis | |
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| Ochratoxin: ortholithiation and anionic Fries rearrangement | |
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| Corydalic acid methyl ester: lateral lithiation | |
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| Fredericamycin A: ortho, lateral and [alpha]-lithiation | |
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| ([plus or minus])-Atpenin B: metallation of an aromatic heterocycle | |
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| Flurbiprofen: metallation with LiCKOR superbases | |
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| California Red Scale Pheromone: [alpha]- and reductive lithiation | |
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| C1-C9 of the Bryostatins: diastereoselective bromine-lithium exchange | |
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| (S)-1-Methyldodecyl acetate, a Drosophila pheromone: (-)-sparteine assisted enantioselective lithiation | |
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| (-)-Paroxetine: (-)-sparteine-promoted asymmetric lithiation and substitution | |
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| References | |
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| Index | |