Polymeric chiral crown ethers, 4. Substituent effects of methyl and phenyl groups in the 3,3′-positions on chiral recognition of poly(crown ether)s synthesized by cyclopolymerization of divinyl ethers derived from 1,1′-bi-2-naphthol†
Polymeric chiral crown ethers, 4. Substituent effects of methyl and phenyl groups in the 3,3′-positions on chiral recognition of poly(crown ether)s synthesized by cyclopolymerization of divinyl ethers derived from 1,1′-bi-2-naphthol†
复制标题
聚合手性冠醚，4. 3,3位甲基和苯基的取代基对由1,1-双-2-萘酚衍生的二乙烯基醚环聚合成的聚冠醚手性识别的影响†
DOI：
10.1002/macp.1989.021900909
复制
发表时间：
1989
期刊：
影响因子：
--
通讯作者：
K. Yokota
中科院分区：
文献类型：
--
作者：
T. Kakuchi;T. Hasegawa;H. Sasaki;Hiroshi Ohmori;K. Yamaguchi;K. Yokota
以(S)-2,2'-双(2-乙烯氧基乙氧基)-3,3'-二甲基-1,1'-联萘[(S)-1b]和(R)-2,2'-双[2-(2-乙烯氧基乙氧基)-乙氧基]-3,3'-二甲基(或3,3'-二苯基)-1,1'-联萘[(R)-3b或(R)-3c]。联萘部分3，3′位的取代基干扰单体(S)-1b聚合时的分子内环化，但对单体(R)-3b和(R)-3c的环聚倾向没有影响。 (R)-3b和(R)-3c[(R)-4b和(R)-4c]的聚合物比3,3'-位没有取代基的(R)-3a[(R)-4a]的聚合物对α-氨基酸如苯甘氨酸、苯丙氨酸、缬氨酸和蛋氨酸具有更高的手性识别能力。 3,3'位上的甲基和苯基取代基无疑充当了额外的屏障，导致手性识别能力的增加，尽管效果低于模型冠醚的结果预期。
Chiral poly(crown ether)s were synthesized by cationic cyclopolymerization of (S)-2,2′-bis(2-vinyloxyethoxy)-3,3′-dimethyl-1,1′-binaphthyl [(S)-1b] and (R)-2,2′-bis[2-(2-vinyloxyethoxy)-ethoxy]-3,3′-dimethyl (or 3,3′-diphenyl)-1,1′-binaphthyl [(R)-3b or (R)-3c]. The substituents in the 3,3′-positions of binaphthyl moiety disturb the intramolecular cyclization in the polymerization of monomer (S)-1b, but have no influence on the cyclopolymerization tendency of monomers (R)-3b and (R)-3c. The polymers from (R)-3b and (R)-3c [(R)-4b and (R)-4c] have a higher ability of chiral recognition towards a-amino acids, such as phenylglycine, phenylalanine, valine, and methionine, than the polymer from (R)-3a [(R)-4a], which has no substituent in 3,3′-positions. The methyl and the phenyl substituents in the 3,3′-positions undoubtedly act as additional barrier causing an increase in the ability of chiral recognition, though the effect is less than expected from the result of model crown ethers.