TEMPERATURE EFFECTS IN ASYMMETRIC DIHYDROXYLATION - EVIDENCE FOR A STEPWISE MECHANISM

被引:138
作者
GOBEL, T
SHARPLESS, KB
机构
[1] Department of Chemistry, Scripps Research Institute, La Jolla, California, 92307
来源
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH | 1993年 / 32卷 / 09期
关键词
D O I
10.1002/anie.199313291
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
For more than 50 years, the accepted opinion was that the dihydroxylation of olefins with OsO4 proceeded by a concerted mechanism [Eq. (a)]. However, if the influence of the reaction temperature on the enantiomeric excesses in asymmetric dihydroxylations is studied, Eyring plots are obtained with inversion points, which is consistent with a stepwise mechanism. (Figure Presented.) Copyright © 1993 by VCH Verlagsgesellschaft mbH, Germany
引用
收藏
页码:1329 / 1331
页数:3
相关论文
共 21 条
[1]  
BOSEKEN J, 1922, RECL TRAV CHIM PAY B, V41, P199
[2]   THE ISOINVERSION PRINCIPLE - A GENERAL-MODEL OF CHEMICAL SELECTIVITY [J].
BUSCHMANN, H ;
SCHARF, HD ;
HOFFMANN, N ;
ESSER, P .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1991, 30 (05) :477-515
[3]  
Buschmann H., 1991, ANGEW CHEM, V103, P480
[4]  
Criegee R, 1942, LIEBIGS ANN CHEM, V550, P99
[5]   Organic osmium compounds [J].
Criegee, R .
ANGEWANDTE CHEMIE, 1938, 51 :0519-0520
[6]  
Criegee R, 1936, LIEBIGS ANN CHEM, V522, P75
[7]   The oxidative fussion of C-C-bonds [J].
Criegee, R .
ANGEWANDTE CHEMIE, 1937, 50 :0153-0155
[8]   The activated complex in chemical reactions [J].
Eyring, H .
JOURNAL OF CHEMICAL PHYSICS, 1935, 3 (02) :107-115
[9]  
GABLE KA, COMMUNICATION
[10]  
HENTGES SG, 1980, J AM CHEM SOC, V102, P5974