AlCl3-Catalyzed Hydrosilylation of Alkynes with Hydropolysilanes†
AlCl3-Catalyzed Hydrosilylation of Alkynes with Hydropolysilanes†
复制标题
AlCl3 催化的炔烃与氢聚硅烷的氢硅烷化†
DOI：
10.1021/om100376d
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发表时间：
2010
期刊：
影响因子：
2.8
通讯作者：
Masato Tanaka
中科院分区：
文献类型：
--
作者：
Nobu Kato;Y. Tamura;Taigo Kashiwabara;T. Sanji;Masato Tanaka
AlCl 3催化氢化低聚硅烷（H（SiMe 2）nR; n = 2−4，R = H，Me，Ph）与1-癸炔和其他炔在温和条件下的加成反应。在大多数反应中，Si−Si键保持完整，以相当优异的产率形成预期的产物，尽管Si−Ph键似乎在条件下部分断裂。芳基乙炔由于Si−Si键断裂而倾向于形成异常产物，但在低温下，加成反应正常进行。1，2-二氢四甲基二硅烷与1-癸炔的反应在0 °C下除去1，2-二癸烯基二硅烷、1，3-二癸烯基三硅烷和其它副产物，而在较低温度下进行的反应干净地进行。1，3-二氢六甲基三硅烷甚至在0 °C下反应更清洁。五甲基二硅烷与1，6-庚二炔的反应以不同的方向进行，导致环化。1，7-辛二炔与1，3-二氢六甲基三硅烷反应以得到聚合物材料。研究了1，2，3-三氢五甲基三硅烷或聚苯基硅烯的反应机理。
AlCl3 catalyzes addition reactions of hydrooligosilanes (H(SiMe2)nR; n = 2−4, R = H, Me, Ph) with 1-decyne and other alkynes under mild conditions. In most reactions the Si−Si bonds remain intact to form anticipated products in fair to excellent yields, although Si−Ph bonds appear to be cleaved partially under the conditions. Arylethynes tend to form abnormal products due to Si−Si bond scission, but at a low temperature, the addition reaction proceeds normally. The reaction of 1,2-dihydrotetramethyldisilane with 1-decyne furnishes 1,2-didecenyldisilane, 1,3-didecenyltrisilane, and other byproducts at 0 °C, while the reaction run at a lower temperature proceeds cleanly. 1,3-Dihydrohexamethyltrisilane reacts more cleanly even at 0 °C. The reaction of pentamethyldisilane with 1,6-heptadiyne proceeds in a different direction, leading to cyclization. 1,7-Octadiyne reacts with 1,3-dihydrohexamethyltrisilane to give a polymeric material. The reaction of 1,2,3-trihydropentamethyltrisilane or poly(phenylsilylene) ...