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

Hanbin Liu; Kai Deng; Theodore Cohen; Kenneth D Jordan

doi:10.1021/ol070453+

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

Org Lett. 2007 May 10;9(10):1911-4. doi: 10.1021/ol070453+. Epub 2007 Apr 18.

Authors

Hanbin Liu¹, Kai Deng, Theodore Cohen, Kenneth D Jordan

Affiliation

¹ Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA.

PMID: 17439226
DOI: 10.1021/ol070453+

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.