The first fluoride-free Hiyama reaction of vinylsiloxanes promoted by sodium hydroxide in water
The first fluoride-free Hiyama reaction of vinylsiloxanes promoted by sodium hydroxide in water
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DOI：
10.1002/adsc.200600262
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发表时间：
2006-10-01
影响因子：
5.4
通讯作者：
Najera, Carmen
中科院分区：
文献类型：
--
作者：
Alacid, Emilio;Najera, Carmen
报道了在无氟条件下，用氢氧化钠水溶液促进乙烯基烷氧基硅烷与芳基溴化物或氯化物的交叉偶联反应，得到苯乙烯。在空气中加入四正丁基溴化铵（TBAB）作为添加剂，在120℃的低温或微波加热条件下，以醋酸钯（II）或4-羟基苯乙酮肟衍生的钯环为催化剂（钯用量0.01-1 mol %）催化反应。在苯乙烯基三乙氧基硅烷的情况下，与芳基或乙烯基溴的偶联发生立体特异性，分别得到相应的二苯乙烯或二烯。这些温和和简单的反应条件防止了不良的聚合产物。
The first cross-coupling reaction between vinylalkoxysilanes and aryl bromides or chlorides promoted by aqueous sodium hydroxide under fluoride-free conditions to provide styrenes is reported. The reaction is catalyzed by palladium(II) acetate or a 4-hydroxyacetophenone oxime-derived palladacycle either under thermal or microwave heating at 120 degrees C with low catalyst loading (0.01-1 mol % of palladium) in the presence of tetra-n-butylammonium bromide (TBAB) as additive in air. In the case of styryltriethoxysilane, the coupling with aryl or vinyl bromides takes place stereospecifically to give the corresponding stilbenes or dienes, respectively. These mild and simple reaction conditions prevent undesirable polymerization of the products.