Organolithiums: Selectivity for Synthesis

摘要: Introduction: scope and overview organolithiums in solution. Regioselective synthesis of by deprotonation: general points lithiation alpha to heteroatoms ortholithiation lateral remote lithiation, beta-lithiation non-aromatic compounds superbases co-operation, competition regioselectivity. X-Li exchange: halogen-lithium exchange tin-lithium chalcogen-lithium phosphorus-lithium exchange. C-X reduction: reductive alkyl aryl halides C-O bonds C-N C-S C-C pi-bonds. Stereoselective stereospecific organolithiums: configurational stability Stereospecific diastereoselective deprotonation enantioselective deprotonation. stereoselective substitution reactions organolithium the presence chiral ligands. Regio- addition intermolecular pi - carbolithiation intramolecular anionic cyclization. Organolithium rearrangements: Shapiro reaction Brook rearrangements [1,2]-Wittig [2,3]-Wittig rearrangements. Organolithiums synthesis: ochratoxin Fries rearrangement corydalic acid methyl ester fredericamycin A ortho, alpha-lithiation (?)-Atpenin B metallation an aromatic heterocycle flurbiprofen with LiCKOR California red scale pheromone alpha- C1-C9 Bryostatins bromine-lithium (S)-1-methyldodecyl acetate, a Drosophila (-)-sparteine assisted (-)-Paroxetine (-)-sparteine-promoted asymmetric substitution.