Phenyl versus ethyl transfer in the addition of organozinc reagents to aldehydes: A theoretical study

被引：71

作者：

Rudolph, J

Rasmussen, T

Bolm, C

Norrby, PO

机构：

[1] Tech Univ Denmark, Dept Chem, DK-2800 Lyngby, Denmark

[2] Rhein Westfal TH Aachen, Inst Organ Chem, D-52074 Aachen, Germany

[3] Lund Univ, Ctr Chem, Dept Theoret Chem, S-22100 Lund, Sweden

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2003年 / 42卷 / 26期

关键词：

alkylation; density functional calculations; transition states; zinc;

D O I：

10.1002/anie.200351150

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The dramatic improvement in diphenylzinc addition to aldehydes that is obtained by adding diethylzinc was investigated by DFT methods. The strong preference for phenyl over ethyl transfer can be understood in terms of overlap with the phenyl 31 system in the transition state (see picture). Reasons for the high ee value in the presence of Et2Zn are discussed.

引用

页码：3002 / 3005

页数：4

共 65 条

[1]

Berrisford D.J., 1995, ANGEW CHEM, V107, P1159

[2] LIGAND-ACCELERATED CATALYSIS [J].