Design and Synthesis of Novel Stereoregular and Optically Active Silicon-containing Polymers

本研究工作的目的是发展立体规整光学活性含硅聚合物的精密合成方法及其性质的控制。我们利用已有的立体选择溴化反应和氢硅烷与硅醇之间的脱氢缩聚反应，合成了具有光学活性和富共映性的聚硅氧烷。我们发现一些含硅单体可以用市售的光学活性固定相进行高效液相色谱分离得到光学纯。聚加成和开环聚合得到光学纯丙基硅烷和硅环丁烯，得到光学活性聚碳硅烷。我们还通过光活性硅锂与光活性氯硅烷的立体选择性亲核反应合成了光活性低硅烷，并用x射线衍射和CD光谱对其立体结构进行了表征。

The purpose of this research work is the development of precision synthetic method of stereoregular and optically active silicon-containing polymers and the control of their properties.We have synthesized optically active and syndiotactic-rich polysiloxanes by application of the reactions, such as stereoselective bromination reaction and dehydrogenative polycondensation reaction between hydrosilanes and silanols, which we have developed before. We found that some silicon-containing monomers can be separated by HPLC with commercially available optically active stationary phase to become optically pure. Polyaddition and ring-opening polymerization of resulting optically pure propargylsilane and silacyclobutene gave optically active polycarbosilanes. We also synthesized optically active oligosilanes by stereoselective nucleophilic reaction of optically active silyllithium and optically active chlorosilane, and characterized their stereostrucutures by X-ray diffraction and CD spectroscopy.