Synthesis of stable and soluble one-handed helical homopoly(substituted acetylene)s without the coexistence of any other chiral moieties via two-step polymer reactions in membrane state: molecular design of the starting monomer.
Synthesis of stable and soluble one-handed helical homopoly(substituted acetylene)s without the coexistence of any other chiral moieties via two-step polymer reactions in membrane state: molecular design of the starting monomer.
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稳定和可溶性的单手螺旋均应（取代的乙炔）的合成，而没有其他手性部分通过膜状态的两步聚合物反应的任何其他手性部分的共存：起始单体的分子设计。
DOI：
10.3390/molecules17010433
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发表时间：
2012-01-04
期刊：
影响因子：
--
通讯作者：
Kaneko T
中科院分区：
文献类型：
--
作者：
Abe Y;Aoki T;Jia H;Hadano S;Namikoshi T;Kakihana Y;Liu L;Zang Y;Teraguchi M;Kaneko T
通过手性单体的不对称诱导聚合，然后在膜态下进行两步聚合物反应，成功合成了一种不与任何其他手性部分共存的可溶且稳定的单手螺旋聚（取代苯乙炔）：（1）去除手性基团（去取代）； (2)在与去取代相同的位置引入非手性长烷基以增强所得单手螺旋聚合物的溶解度(再取代)。起始手性单体应具有四个特征取代基：（i）与容易水解的间隔基团键合的手性基团； (ii) 两个羟基； (iii)手性基团和聚合基团之间的长刚性疏水间隔基； (iv) 靠近手性基团的长非手性基团。选择碳酸酯作为间隔基团。在膜态两步聚合物反应之前和之后，两个羟基形成分子内氢键，稳定溶液中的单手螺旋结构。刚性长疏水间隔基苯乙炔基苯基增强了起始聚合物的溶解度，并在不对称诱导聚合中实现了从手性侧基到主链的有效手性诱导。手性基团附近的长烷基避免了膜的收缩，并在去除手性基团后保持了膜状态下的再取代反应活性。尽管不存在任何其他手性部分，分配给所得最终聚合物中主链的CD信号的g值(g=([θ]/3,300)/ε)几乎与起始聚合物相同。此外，由于溶液中的单手螺旋结构是通过分子内氢键维持的，因此首次实现了在溶液的CD中直接观察最终均聚物的单手螺旋性。
A soluble and stable one-handed helical poly(substituted phenylacetylene) without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer followed by two-step polymer reactions in membrane state: (1) removing the chiral groups (desubstitution); and (2) introduction of achiral long alkyl groups at the same position as the desubstitution to enhance the solubility of the resulting one-handed helical polymer (resubstitution). The starting chiral monomer should have four characteristic substituents: (i) a chiral group bonded to an easily hydrolyzed spacer group; (ii) two hydroxyl groups; (iii) a long rigid hydrophobic spacer between the chiral group and the polymerizing group; (iv) a long achiral group near the chiral group. As spacer group a carbonate ester was selected. The two hydroxyl groups formed intramolecular hydrogen bonds stabilizing a one-handed helical structure in solution before and after the two-step polymer reactions in membrane state. The rigid long hydrophobic spacer, a phenylethynylphenyl group, enhanced the solubility of the starting polymer, and realized effective chiral induction from the chiral side groups to the main chain in the asymmetric-induced polymerization. The long alkyl group near the chiral group avoided shrinkage of the membrane and kept the reactivity of resubstitution in membrane state after removing the chiral groups. The g value (g = ([θ]/3,300)/ε) for the CD signal assigned to the main chain in the obtained final polymer was almost the same as that of the starting polymer in spite of the absence of any other chiral moieties. Moreover, since the one-handed helical structure was maintained by the intramolecular hydrogen bonds in a solution, direct observation of the one-handed helicity of the final homopolymer has been realized in CD for the solution for the first time.
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影响因子：
5.5
作者：
Jia, Hongge;Teraguchi, Masahiro;Marwanta, Edy
通讯作者：
Marwanta, Edy
影响因子：
5.5
作者：
Kakuchi, T;Narumi, A;Yokota, K
通讯作者：
Yokota, K
DOI：
10.1002/anie.199401881
发表时间：
1994-02-01
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH
影响因子：
--
作者：
WULFF, G;SCHMIDT, H;ZENTEL, R
通讯作者：
ZENTEL, R
影响因子：
1.6
作者：
Hadano, Shingo;Teraguchi, Masahiro;Aoki, Toshiki
通讯作者：
Aoki, Toshiki
影响因子：
5.5
作者：
Kaneko, Takashi;Umeda, Yasuhiro;Aoki, Toshiki
通讯作者：
Aoki, Toshiki