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.

引用

页码：2101 / 2104

页数：4

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