American Chemical Society
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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

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journal contribution
posted 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.