Silylboranes bearing dialkylamino groups on silicon as silylene equivalents: palladium-catalyzed regioselective synthesis of 2,4-disubstituted siloles.
Silylboranes bearing dialkylamino groups on silicon as silylene equivalents: palladium-catalyzed regioselective synthesis of 2,4-disubstituted siloles.
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DOI：
10.1021/ja073896h
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发表时间：
2008-01
影响因子：
15
通讯作者：
Toshimichi Ohmura;K. Masuda;M. Suginome
中科院分区：
文献类型：
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作者：
Toshimichi Ohmura;K. Masuda;M. Suginome
在钯催化下，硅原子上含有二烷氨基的硅基频那科硼烷作为合成硅烯的等价物与末端炔烃反应，高产率地生成了2，4-二取代硅烷。研究发现，硅原子上的氨基对反应非常重要；在使用硅原子上带有芳基、氯基或烷氧基的硅基频碳硼烷的反应中，没有发现硅烷产物。1，1-二甲基-2，4-二苯基硅烷经位选择性溴化，再与芳基炔基三丁基锡偶联，得到了总收率较高的新型π共轭硅分子。
Silylpinacolboranes bearing dialkylamino groups on the silicon atom served as synthetic equivalents of silylene in palladium-catalyzed reactions with terminal alkynes, leading to the formation of 2,4-disubstituted siloles in high yield. It was found that the amino group on the silicon atom was critically important for the reaction; no silole products were found in reactions using silylpinacolboranes carrying aryl, chloro, or alkoxy groups on the silicon atoms. Site-selective bromination of 1,1-dimethyl-2,4-diphenylsilole followed by Migita−Kosugi−Stille coupling with (arylalkynyl)tributylstannanes gave novel π-conjugated siloles with good total yields.