Separation of Optically Active Ethynylsilane Derivatives and Their Polymerization by Transition-Metal Catalysts
作者:Yusuke Kawakami、Masakatsu Omote、Ichiro Imae、Eiji Shirakawa
DOI:10.1021/ma0301101
日期:2003.10.1
Optically pure (−)-(4-bromophenyl)ethynylmethyl(1-naphthyl)silane [(−)-1], (−)-1,2-diethynyl-1,2-dimethyl-1,2-di(1-naphthyl)disilane [(−)-2], and (+)-1,2-diethynyl-1,2-dimethyl-1,2-diphenyldisilane [(+)-3] were separated by a chromatographic technique on an optically active stationary phase. Polymerization via Heck reaction or dimerization of bis(ethynyl) groups of these compounds gave optically active
光学纯的( - ) - (4-溴苯基)ethynylmethyl(1-萘基)硅烷[ (- )-1 ],( - ) - 1,2-二乙炔基-1,2-二甲基-1,2-二(1-通过色谱技术在光学活性上分离萘基)乙硅烷[ (- )- 2 ]和(+)-1,2-二乙炔基-1,2-二甲基-1,2-二苯基乙硅烷[ (+)-3 ]固定相。通过Heck反应的聚合或这些化合物的双(乙炔基)基团的二聚,得到旋光聚合物。聚合物的结构通过1 H,13 C和29 Si NMR光谱表征。聚(1)和聚(2)具有规则的化学结构。在聚(3),(E)-ene-yne与(E)-ene-(E)-ene和yne-yne结构混合。关于硅原子的构型,所有聚合物均被认为是立构规整的。测量溶液中的光学性质。尽管光学活性聚合物的电子吸收光谱和荧光光谱与消旋聚合物相比没有变化,但是圆二色性光谱显示出负的Cotton效应。