Stereoselectivity and stereospecificity of cyclopropanation reactions with stable (phosphanyl)(silyl)carbenes

被引：45
|
作者：
Goumri-Magnet, S [1 ]
Kato, T [1 ]
Gornitzka, H [1 ]
Baceiredo, A [1 ]
Bertrand, G [1 ]
机构：
[1] Univ Toulouse 3, Lab Heterochim Fondamentale & Appl, F-31062 Toulouse 04, France
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2000年 / 122卷 / 18期
关键词：
D O I：
10.1021/ja994408b
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The stable (phosphanyl)(silyl)carbenes la,b react efficiently with various electron-poor alkenes [methyl acrylate, 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene, styrene, (Z)- and (E)-2-deuteriostyrene, (E)-t-BuOC(O)CH=CHC(O)OEt, and (E)-Me2NCOCH=CHCO2Me] giving the corresponding cyclopropanes in good yields. The stereochemical outcome was such that all monosubstituted alkenes gave exclusively the syn isomer (with respect to the phosphanyl group), and the addition of disubstituted alkenes was totally stereospecific. The high stereoselectivity observed was ascribed to a secondary orbital interaction (LUMOcarbene-HOMOalkene) similar to that explaining the endo-rule in Diels-Alder reactions.
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页码：4464 / 4470
页数：7
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