ol070453+_si_001.pdf (613.72 kB)
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
journal contributionposted on 2020-04-02, 16:20 authored by Hanbin Liu, Kai Deng, Theodore Cohen, Kenneth D. Jordan
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.