title: Computational study of the stereochemistry of intramolecular carbolithiation of an alkene by a secondary alkyllithium: stereochemistry change caused by a single THF molecule of solvation.
abstract: Theoretical calculations reveal that the 40:1 ratio of trans- to cis-2-methylcyclopentylmethyllithium formed in the cyclization of 6-lithio-1-heptene by intramolecular carbolithiation is due to steric crowding in the transition state for the cis-cyclization pathway when a single THF molecule complexes the lithium cation. In the absence of this specific solvation, the cis-cyclization pathway is predicted to be slightly favored.
authors: Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA.
authors: Hanbin
authors: H
authors: Liu
authors: Kai
authors: K
authors: Deng
authors: Theodore
authors: T
authors: Cohen
authors: Kenneth D
authors: KD
authors: Jordan