Chiral 1-Methylpropargyl Alcohol: A Simple and Powerful Helical Source for Substituted Polyacetylenes
Chiral 1-Methylpropargyl Alcohol: A Simple and Powerful Helical Source for Substituted Polyacetylenes
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DOI：
10.1021/ma0629642
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发表时间：
2007-02
期刊：
影响因子：
5.5
通讯作者：
Yuji Suzuki;M. Shiotsuki;F. Sanda;T. Masuda
中科院分区：
文献类型：
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作者：
Yuji Suzuki;M. Shiotsuki;F. Sanda;T. Masuda
以(NbD)Rh+[η6-C6H5B-(C6H5)3]为催化剂，聚合了(S)-和(R)-1-甲基丙叉醇[(S)-1和(R)-1]及其酯类衍生物[(S)-2和(R)-2]，得到了相对分子质量适中的取代聚乙炔。核磁共振氢谱表明，聚合物具有顺式立体规则结构。大的旋光度和清晰的CD信号表明，这些聚合物具有螺旋结构，主要是单手螺旋感觉，通过主链附近含有手性基团的侧链之间的空间排斥来稳定。
(S)- and (R)-1-methylpropargyl alcohols [(S)-1 and (R)-1] and their ester derivatives (S)- and (R)-1-methylpropargyl hexanoates [(S)-2 and (R)-2] were polymerized using (nbd)Rh+[η6-C6H5B-(C6H5)3] as catalyst to afford the corresponding substituted polyacetylenes with moderate molecular weights in good yields. The polymers possessed cis-stereoregular structures according to 1H NMR. Large optical rotations and clear CD signals demonstrated that these polymers took a helical structure with predominantly one-handed screw sense, stabilized by steric repulsion between the side chains containing chiral groups adjacent to the main chain.