Organolithiums: Selectivity for Synthesis

ISBN: 9780080432625 出版年：2002 页码：401 Clayden, Jonathan Pergamon_Series

Introduction: scope and overview organolithiums in solution. Regioselective synthesis of organolithiums by deprotonation: general points lithiation alpha to heteroatoms ortholithiation lateral lithiation remote lithiation, and beta-lithiation of non-aromatic compounds superbases co-operation, 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 pi-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 pi bonds - carbolithiation intramolecular addition and substitution reactions - anionic cyclization. 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 alpha-lithiation (?)-Atpenin B - metallation of an aromatic heterocycle flurbiprofen - metallation with LiCKOR superbases California red scale pheromone - alpha- and reductive lithiation C1-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.