title: A theoretical investigation into the inversion barrier of dipole-stabilized alpha-aminoorganolithiums.
abstract: [reaction: see text] 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 alpha-aminoorganolithiums.
authors.affiliation: Department of Physics, Stockholm University, SCFAB, S 106 91 Stockholm, Sweden. haeffner@physto.se
authors.forename: Fredrik
authors.initials: F
authors.lastname: Haeffner
authors.forename: Peter
authors.initials: P
authors.lastname: Brandt
authors.forename: Robert E
authors.initials: RE
authors.lastname: Gawley