An efficient catalytic asymmetric epoxidation method

被引:573
作者
Wang, ZX [1 ]
Tu, Y [1 ]
Frohn, M [1 ]
Zhang, JR [1 ]
Shi, Y [1 ]
机构
[1] COLORADO STATE UNIV,DEPT CHEM,FT COLLINS,CO 80523
关键词
D O I
10.1021/ja972272g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
This article describes a highly effective catalytic asymmetric epoxidation method for olefins using potassium peroxomonosulfate (Oxone, Dupont) as oxidant and a fructose-derived ketone (1) as catalyst. High enantioselectivies have been obtained for trans-disubstituted and trisubstituted olefins which can bear functional groups such as tributylsilyl ether, acetal, chloride, and ester. The enantiomeric excesses for cis-olefins and terminal olefins are not high yet. The current epoxidation shows that the catalyst efficiency is enhanced dramatically upon raising the pH. Mechanistic studies show that the epoxidation mainly proceeds via a spiro transition state, which provides a model for predicting the stereochemical outcome of the reaction. The planar transition state is likely to be the main competing pathway. The extent of the involvement of the planar mode is subject to the steric effect of the alkyl groups on the olefins.
引用
收藏
页码:11224 / 11235
页数:12
相关论文
共 84 条
[81]   EPOXIDATION OF OLEFINS USING METHYL(TRIFLUOROMETHYL)DIOXIRANE GENERATED IN-SITU [J].
YANG, D ;
WONG, MK ;
YIP, YC .
JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (12) :3887-3889
[82]   A C-2 symmetric chiral ketone for catalytic asymmetric epoxidation of unfunctionalized olefins [J].
Yang, D ;
Yip, YC ;
Tang, MW ;
Wong, MK ;
Zheng, JH ;
Cheung, KK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (02) :491-492
[83]   Highly enantioselective epoxidation of trans-stilbenes catalyzed by chiral ketones [J].
Yang, D ;
Wang, XC ;
Wong, MK ;
Yip, YC ;
Tang, MW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (45) :11311-11312
[84]   ENANTIOSELECTIVE EPOXIDATION OF UNFUNCTIONALIZED OLEFINS CATALYZED BY (SALEN)MANGANESE COMPLEXES [J].
ZHANG, W ;
LOEBACH, JL ;
WILSON, SR ;
JACOBSEN, EN .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (07) :2801-2803