A DFT-derived model predicts solvation-dependent configurational stability of organolithium compounds: a case study of a chiral alpha-thioallyllithium compound

Density functional theory calculations (B3LYP/6-31+G*) were performed to evaluate a model previously published by us which suggests that aggregation and solvation of organolithium compounds can be of large importance for their configurational stability. In this study, we demonstrate how THF solvation of the monomer of a chiral alpha-thioallyllithium compound impedes the racemization, while upon dimerization the inversion process accelerates. These findings agree with experiments performed by Hoppe and co-workers. These findings may be used to further develop organolithium compounds which should be designed to resist aggregation and efficient transition-state solvation.