THE STEREOCHEMISTRY OF THE REACTION OF ALLYLSILANES WITH OSMIUM-TETROXIDE AND OF THE EPOXIDATION AND METHYLENATION OF ALLYLSILANES

被引:29
作者
FLEMING, I
LAWRENCE, NJ
SARKAR, AK
THOMAS, AP
机构
[1] University Chemical Laboratory, Cambridge CB2 1EW, Lensfield Road
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 1992年 / 24期
关键词
D O I
10.1039/p19920003303
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The allylsilanes E-7 react with osmium tetroxide, with m-chloroperbenzoic acid and with the Yamamoto methylenating reagent to give the diols 8 and 9, the epoxides 10 and 11, and the cyclopropanes 12 and 13, respectively. The reactions are more selective for the formation of the even-numbered diastereoisomers when the substituent on the stereogenic centre is an isopropyl or phenyl group than when it is a methyl group. The corresponding Z-allylsilanes, Z-7, are even more selective in this sense, giving more of the diol 14 than of 15, and only the epoxides 16 and the cyclopropanes 18. The ground-state conformation, as measured by the coupling constants in 24 and 25, correlates with the diastereoselectivity, as does a simple calculation of the relative energies of the two most appropriate conformations of the starting materials.
引用
收藏
页码:3303 / 3308
页数:6
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