Organolithiums: Selectivity for Synthesis
- J Clayden, Department of Chemistry University of Manchester Manchester UK
- Published: July 2002
- Imprint: PERGAMON
- ISBN: 978-0-08-043261-8
"Organolithiums: Selectivity for Synthesis" is recommended for every chemist who wishes to become thoroughly acquainted with the potential of organolithium chemistry. Jonathan Clayden has succeeded in conveying this knowledge with succinct commentaries supported by appropriate examples.
ORGANIC CHEMISTRY, 2005
Table of ContentsIntroduction.Scope and overview. Organolithiums in solution.
Regioselective Synthesis of Organolithiums by Deprotonation. General points. Lithiation &agr; to heteroatoms. Ortholithiation. Lateral lithiation. Remote lithiation, and &Bgr;-lithiation of non-aromatic compounds. Superbases. Cooperation, competition and regioselectivity.
Regioselective Synthesis of Organolithiums by X-Li Exchange.Halogen-lithium exchange. Tin-lithium exchange. Chalcogen-lithium exchange. Phosphorus-lithium exchange.
Regioselective Synthesis of Organolithiums by C-X Reduction.Reductive lithiation of alkyl and aryl halides. Reductive lithiation of C-O bonds. Reductive lithiation of C-N bonds. Reductive lithiation of C-S bonds. Reductive lithiation of C-C bonds and &pgr;-bonds.
Stereoselective and Stereospecific Synthesis of Organolithiums.Configurational stability of organolithiums. Stereospecific synthesis of organolithiums by X-Li exchange. Diastereoselective deprotonation. Enantioselective deprotonation.
Stereospecific and Stereoselective Substitution Reactions of Organolithiums.Stereospecific reactions of organolithium compounds. Stereoselective substitution in the presence of chiral ligands.
Regio- and Stereoselective Addition Reactions of Organolithiums. Intermolecular addition to &pgr; bonds: Carbolithiation.Intramolecular addition and substitution reactions: anionic cyclisation.
Organolithium Rearrangements.Shapiro reaction. Brook rearrangements. [1,2]-Wittig Rearrangements.[2,3]-Wittig Rearrangements.
Organolithiums in Synthesis.Ochratoxin: ortholithiation and anionic Fries rearrangement. Corydalic acid methyl ester: lateral lithiation.Fredericamycin A: ortho, lateral and &agr;-lithiation.(?)-Atpenin B: metallation of an aromatic heterocycle. Flurbiprofen: metallation with LiCKOR superbases. California Red Scale Pheromone: &agr;- and reductive lithiationC1-C9 of the Bryostatins: diastereoselective bromine-lithium exchange.(S)-1-Methyldodecyl acetate, a Drosophila pheromone: (-)-sparteine assisted enantioselective lithiation.(-)-Paroxetine: (-)-sparteine-promoted asymmetric lithiation and substitution.