This volume, number 23 in the ""Tetrahedron Organic Chemistry"" series, presents organolithium chemistry from the perspective of a synthetic organic chemist, drawing from the synthetic literature to present a unified overview of how organolithiums can be used to make molecules. The development of methods for the regioselective synthesis of organolithiums has replaced their image of indiscriminate high reactivity with one of controllable and subtle selectivity. Organolithium chemistry has a central role in the selective construction of C-C bonds in both simple and complex molecules, and for example has arguably overtaken aromatic electrophilic substitution as the most powerful method for regioselective functionalisation of aromatic rings. The twin themes of reactivity and selectivity run through the book, which reviews the ways by which organolithiums may be formed and the ways in which they react. Topics include advances in directed metallation, reductive lithiation and organolithium cyclisation reactions, along with a discussion of organolithium stereochemistry and the role played by ligands such as (-)-sparteine.
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.
Reviews for Organolithiums: Selectivity for Synthesis
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
