Asymmetric anionic polymerization of 7-cyano-7-phenyl-1,4-benzoquinone methide

被引：0
作者：
Risa Nakagawa
Takahiro Uno
Masataka Kubo
Takahito Itoh
机构：
[1] Mie University,Division of Chemistry for Materials, Graduate School of Engineering
[2] Mie University,Graduate School of Regional Innovation Studies
来源：
Polymer Bulletin | 2012年 / 68卷
关键词：
Asymmetric anionic polymerization; Optically active polymer; Chiral initiator; Stereocontrol; Quinone methide; Optical resolution;
D O I：
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摘要：
Asymmetric anionic polymerizations of a prochiral monomer, 7-cyano-7-phenyl-1,4-benzoquinone methide (3), using chiral initiators were performed under various conditions, and optically active polymers having configurational chirality in the main chain were obtained though their specific rotation values are quite small. The optically active polymer with a negative specific rotation value of −4.4° was obtained by polymerization of 3 with a lithium isopropylphenoxide (iPrPhOLi)/(−)-sparteine ((−)-Sp) in a mixture solution of dichloromethane/toluene ratio of 30/70 (in vol%) at −40 °C. Stereostructures of 1-mer, 2-mer, and oligomers obtained by asymmetric anionic oligomerization of 3 with iPrPhOLi/(−)-Sp were examined in detail. It was found that the stereoselectivity turned out to be the opposite between the initiation reaction and the propagation one.
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页码：1831 / 1844
页数：13
相关论文
共 60 条
[1]  
Okamoto Y(1994)Asymmetric polymerization Chem Rev 94 349-372
[2]  
Nakano T(1995)A helical polymer with a cooperative response to chiral information Science 268 1860-1866
[3]  
Green MM(2001)Synthetic helical polymers: conformation and function Chem Rev 101 4013-4038
[4]  
Peterson NC(2001)Chiral architectures from macromolecular building blocks Chem Rev 101 4039-4070
[5]  
Sato T(2001)Optically active polysilylenes: state-of-the-art chiroptical polymers Macromol Rapid Commun 22 539-563
[6]  
Teramoto A(2008)Chirality-responsive helical polymers Macromolecules 41 3-12
[7]  
Cook R(2000)Asymmetric anionic polymerization of maleimides bearing bulky substituents J Polym Sci Part A 36 310-320
[8]  
Lifson S(1964)Quinone methides Quart Rev (Lond) 18 347-360
[9]  
Nakano T(1983)Convenient monoketalization of 1,4-cyclohexanedinone. Synthesis of new quinine methides J Org Chem 48 129-131
[10]  
Okamoto Y(1993)Synthesis and polymerization of 7-(alkoxycarbonyl)-7-cyano-1,4-benzoquinone methides Macromolecules 26 1213-1220
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