Description This book, Volume 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 recent 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.
Audience
For graduate students or researchers who wish to use organolithiums to construct molecules, or to understand more about organolithium
stereochemistry and reactivity and the mechanisms of their reactions.
Contents
Introduction.
Scope and overview. Organolithiums in solution.
Regioselective Synthesis of Organolithiums by Deprotonation.
General points. Lithiation α to heteroatoms. Ortholithiation. Lateral lithiation. Remote lithiation, and Β-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 π-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 π bonds:
Carbolithiation.
Intramolecular addition and substitution reactions: anionic cyclisation.
Organolithiums in Synthesis.
Ochratoxin:
ortholithiation and anionic Fries rearrangement. Corydalic acid methyl ester: lateral lithiation.
Fredericamycin A: ortho, lateral and α-lithiation.
(?)-Atpenin B: metallation of an aromatic heterocycle.
Flurbiprofen: metallation with LiCKOR superbases.
California
Red Scale Pheromone: α- 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.
Books and book related electronic products are priced in US dollars (USD), euro (EUR), and Great Britain Pounds (GBP). USD prices apply to the Americas and Asia Pacific. EUR prices apply in Europe and the Middle East. GBP prices apply to the UK and all other countries.
Home | Elsevier Sites | Privacy Policy | Terms and Conditions | Feedback | Site Map | A Reed Elsevier Company