A Theoretical Investigation into the Inversion Barrier of Dipole-Stabilized α-Aminoorganolithiums
- 17 May 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Organic Letters
- Vol. 4 (12) , 2101-2104
- https://doi.org/10.1021/ol026041c
Abstract
Results from density functional theory calculations (B3LYP/6-31+G*) suggest that inversion of the monomer of 2-lithio-N-formylpyrrolidine (2) in coordinating ethereal solvent occurs with an activation barrier of 15.7 kcal/mol, while the inversion of the monomer in a noncoordinating hydrocarbon solvent is considerably slower. However, aggregation into a trimer in hydrocarbon solvent restores the low inversion barrier. This study suggests that solvation and aggregation may influence the mechanism and rate of racemization of dipole-stabilized α-aminoorganolithiums.This publication has 16 references indexed in Scilit:
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