Kinetic and stereochemical evidence for the involvement of only one proline molecule in the transition states of proline-catalyzed intra- and intermolecular aldol reactions

被引：383
作者：
Hoang, L
Bahmanyar, S
Houk, KN
List, B
机构：
[1] Scripps Res Inst, Dept Mol Biol, La Jolla, CA 92037 USA
[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2003年 / 125卷 / 01期
关键词：
D O I：
10.1021/ja028634o
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Contrary to the widely accepted mechanism of the Hajos-Parrish-Eder-Sauer-Wiechert reaction, we have obtained evidence for the involvement of only one proline molecule in the transition states of both inter- and intramolecular aldol reactions. Our conclusions are based on kinetic measurements and the absence of nonlinear and dilution effects on the asymmetric catalysis, and are supported by B3LYP/6-31G* calculations. Complementary to recent theoretical studies, our results provide the foundation of a unified enamine catalysis mechanism of proline-catalyzed inter- and intramolecular aldol reactions. Copyright © 2003 American Chemical Society.
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页码：16 / 17
页数：2
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