A theoretical investigation into the inversion barrier of dipole-stabilized α-aminoorganolithiums

被引：17
|
作者：
Haeffner, F [1 ]
Brandt, P
Gawley, RE
机构：
[1] Stockholm Univ, Dept Phys, SCFAB, S-10691 Stockholm, Sweden
[2] Royal Inst Technol, Dept Organ Chem, S-10044 Stockholm, Sweden
[3] Univ Miami, Dept Chem, Coral Gables, FL 33124 USA
来源：
ORGANIC LETTERS | 2002年 / 4卷 / 12期
关键词：
D O I：
10.1021/ol026041c
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
[GRAPHIC] 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.
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页码：2101 / 2104
页数：4
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