乙烯基三（三甲基硅基）硅烷：用于日山偶联反应的底物。
Vinyl Tris(trimethylsilyl)silanes: Substrates for Hiyama Coupling.
作者信息
Wang Zhizhong, Pitteloud Jean-Philippe, Montes Lucresia, Rapp Magdalena, Derane Djenny, Wnuk Stanislaw F
机构信息
Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, USA.
出版信息
Tetrahedron. 2008 May 26;64(22):5322-5327. doi: 10.1016/j.tet.2008.03.024.
The oxidative treatment of vinyl tris(trimethylsilyl)silanes with hydrogen peroxide in aqueous sodium hydroxide in tetrahydrofuran generates reactive silanol or siloxane species that undergo Pd-catalyzed cross-couplings with aryl, heterocyclic and alkenyl halides in the presence of Pd(PPh(3))(4) and tetrabutylammonium fluoride. Hydrogen peroxide and base are necessary for the coupling to occur while activation of the silanes with fluoride is not required. The conjugated and unconjugated tris(trimethylsilyl)silanes serve as good cross-coupling substrates. The (E)-silanes undergo coupling with retention of stereochemistry while coupling of (Z)-silanes occurred with lower stereoselectivity to produce an E/Z mixture of products.
在四氢呋喃中，乙烯基三（三甲基硅基）硅烷在氢氧化钠水溶液中用过氧化氢进行氧化处理，会生成活性硅醇或硅氧烷物种，这些物种在Pd(PPh(3))(4)和四丁基氟化铵存在下，能与芳基、杂环和烯基卤化物发生钯催化的交叉偶联反应。偶联反应发生时，过氧化氢和碱是必需的，而不需要用氟化物对硅烷进行活化。共轭和非共轭的三（三甲基硅基）硅烷都是良好的交叉偶联底物。（E）-硅烷在偶联反应中保持立体化学构型，而（Z）-硅烷的偶联反应立体选择性较低，会生成E/Z混合产物。
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