Asymmetric Anionic Polymerization of (S)-(−)-N-Maleoyl-L-Valine Methyl Ester
Asymmetric Anionic Polymerization of (S)-(−)-N-Maleoyl-L-Valine Methyl Ester
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DOI：
10.1295/polymj.36.878
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发表时间：
2004-11
期刊：
影响因子：
2.8
通讯作者：
Y. Zhang;K. Onimura;H. Tsutsumi;T. Oishi
中科院分区：
文献类型：
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作者：
Y. Zhang;K. Onimura;H. Tsutsumi;T. Oishi
以L-缬氨酸和顺丁烯二酸酐为原料，合成了一种N-取代马来酰亚胺（RMI），手性（S）-（−）-N-马来酰-L-缬氨酸甲酯（（S）-（−）-MVMI），比旋光度[α]435 = −102.2°。通过（S）-（-）-MVMI与二乙基锌（Et 2 Zn）/（S，S）-的不对称阴离子聚合，得到了高比旋度的聚合物[α]435 = −340.4°和[α]435 = −292.2°。（1-乙基亚丙基）双（4-苄基-2-恶唑啉）（（S，S）-Bnbox）（1.0/1.2）和Et 2 Zn/（-）-鹰爪豆碱（Sp）（1.0/1.2）引发剂。用凝胶渗透色谱（GPC）、圆二色谱（CD）和~（13）CNMR研究了具有苏式-双等规结构的聚合物主链中的不对称诱导。
A kind of N-substituted maleimide (RMI), chiral (S)-(−)-N-maleoyl-L-valine methyl ester ((S)-(−)-MVMI) was synthesized successfully from L-valine and maleic anhydride with a specific rotation of [α]435 = −102.2°. The polymers of high specific rotations of [α]435 = −340.4° and [α]435 = −292.2° were obtained by the asymmetric anionic polymerizations of (S)-(−)-MVMI with diethylzinc (Et2Zn)/(S,S)-(1-ethylpropylidene)bis(4-benzyl-2-oxazoline) ((S,S)-Bnbox) (1.0/1.2) and Et2Zn/(−)-sparteine (Sp) (1.0/1.2) initiators, respectively. Asymmetric inductions in the main chains of polymers with threo-diisotactic structures were investigated by the measurements of gel permeation chromatography (GPC), circular dichroisms (CD), and 13C NMR.