Regio- and Stereocontrolled Hydrosilylation Polyaddition Catalyzed by RhI(PPh3)3. Syntheses of Polymers Containing (E)- or (Z)-Alkenylsilane Moieties
Regio- and Stereocontrolled Hydrosilylation Polyaddition Catalyzed by RhI(PPh3)3. Syntheses of Polymers Containing (E)- or (Z)-Alkenylsilane Moieties
复制标题
RhI(PPh3)3 催化的区域和立体控制氢化硅烷化加聚。
DOI：
10.1021/ma9913360
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发表时间：
2000
期刊：
影响因子：
--
通讯作者：
T. Hiyama
中科院分区：
文献类型：
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作者：
A. Mori;E. Takahisa;H. Kajiro;Y. Nishihara;T. Hiyama
近年来，人们对主链上含有π共轭聚（芳烯-乙烯烯）基团的聚合物的电导率和电致发光等性能越来越感兴趣。在聚合物中掺入有机硅也引起了人们的注意，人们已经设计和合成了各种各样的含硅聚合物。尽管对聚合物进行了大量的研究，但很少有研究致力于提供高度选择性地形成e -乙烯和z -乙烯的立体化学控制。另一方面，我们报道了在RhCl (PPh3) 3/NaI或RhI (PPh3) 3的催化下，1-炔的立体发散硅氢化反应，如方案1所示，分别以高度区域和立体控制的方式合成了e -和z -烯基硅烷。这些发现，如果适用于这些聚合物的合成，将导致立体化学控制问题的解决。
There has recently been increasing interest in polymers with π-conjugation bearing poly (arylene-vinylene) moieties in the main chain in connection with properties such as conductivity1 and electroluminescence. 2 Incorporation of organosilicon moieties into the polymer has also attracted attention and a wide variety of such silicon-containing polymers have been designed and synthesized. 3 Despite much effort on the polymers few studies have been devoted to providing the stereochemical control that would form the E-and Z-vinylenes highly selectively.On the other hand, we reported that stereodivergent hydrosilylation of 1-alkynes, as shown in Scheme 1, by the catalysis of RhCl (PPh3) 3/NaI or RhI (PPh3) 3 enabled the syntheses of E-and Z-alkenylsilanes, respectively, in a highly regio-and stereocontrolled manner. 4 The findings, if applicable to the syntheses of such polymers, would lead to a solution of the issue of stereochemical control.