Synthesis of poly(Nε-phenoxycarbonyl-l-lysine) by polycondensation of activated urethane derivative and its application for selective modification of side chain with amines
Synthesis of poly(Nε-phenoxycarbonyl-l-lysine) by polycondensation of activated urethane derivative and its application for selective modification of side chain with amines
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DOI：
10.1002/pola.29230
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发表时间：
2018-11-15
影响因子：
--
通讯作者：
Endo, Takeshi
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文献类型：
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作者：
Akbulut, Huseyin;Ando, Shota;Endo, Takeshi
本文报道了Nα，N-双(苯氧甲酰基)-L赖氨酸在N，N-二甲基乙酰胺中以伯胺为引发剂，在50℃下选择性地消除苯酚和二氧化碳的链式缩聚反应，合成了侧链上N-β-苯氧羰基保护的聚(L-赖氨酸)。在优化反应条件后，通过调节单体与胺引发剂的投料比，在缩聚过程中加入醋酸，抑制了聚L-赖氨酸氨基末端与聚合物侧链上的N-表硅酮-苯氧羰基之间的链间偶联，从而有效地实现了预期的多肽相对分子质量和窄分散性。此外，利用侧链上可能具有反应性的N-表硅基-苯氧羰基部分，伯胺类、仲胺类和芳香胺类化合物通过尿素键的亲核反应有效地实现了后聚合修饰，为合成选择性侧链功能化的聚L赖氨酸样品提供了有利的平台。(C)2018年威利期刊公司J.Polym。科学，A部分：多晶硅。化学。2018、56、2522-2530
We report a methodology for the synthesis of N epsilon-phenoxycarbonyl-protected poly(l-lysine) on the side chain by chain growth polycondensation of N alpha,N epsilon-bis(phenoxycarbonyl)-l-lysine proceeded through the selective elimination of phenol and CO2 from the N alpha phenoxycarbonyl moiety at 50 degrees C in N,N-dimethylacetamide in the presence of a primary amine used as an initiator. After optimization of reaction condition, the addition of acetic acid during polycondensation proved effective for the realization of the predicted molecular weight and narrow dispersity of the corresponding polypeptide by adjusting the feed ratio of monomer to the amine initiator because of the suppression of interchain coupling that occurs between the amino terminus of poly(l-lysine) and the N epsilon-phenoxycarbonyl group on the polymer side chains. Furthermore, taking advantage of the potentially reactive N epsilon-phenoxycarbonyl moiety on the side chain, post-polymerization modification was effectively achieved by the nucleophilic reaction of amine compounds including primary, secondary, and aromatic amines through the formation of urea linkage, providing a useful platform for synthesis of selective side chain functionalization of poly(l-lysine) samples. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2522-2530