Phosgene-Free Synthesis of Poly(L-cysteine) Containing Styrene Moiety as a Reactive Function
Phosgene-Free Synthesis of Poly(L-cysteine) Containing Styrene Moiety as a Reactive Function
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DOI：
10.1002/macp.201700078
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发表时间：
2017-09-01
影响因子：
2.5
通讯作者：
Endo, Takeshi
中科院分区：
文献类型：
--
作者：
Akbulut, Huseyin;Yamada, Shuhei;Endo, Takeshi
通过一种无酶基因的方法，开发了一种新的合成可用于后聚合修饰的N-羧酸酐前体的方法，提供了一种在非常温和的反应条件下获得肽单体的安全和绿色的方法。通过4-乙烯基苄基-L-半胱氨酸的N-苯氧基羰基衍生物（NPC-Cys（VBn））的缩聚反应制备带有反应性苯乙烯部分的均聚物和共聚物，其中消除苯酚和CO 2，同时改变与伯胺引发剂的进料比，以得到相应的多肽，而没有苯乙烯部分的任何降解。苯乙烯部分的后聚合改性通过使用1，4-双（3-巯基丁基氧基）丁烷的自由基加成或硫醇-烯（光）点击反应进行，导致形成交联多肽。NPC-Cys（VBn）的预聚合修饰通过与苄基氨基甲酸酯的点击反应作为模型化合物也证明了侧链官能化以制备用于多肽合成的新单体。
A novel approach toward the synthesis of N-carboxyanhydride precursor available for postpolymerization modification has been developed through a phosgene-free method offering a safer and green way to obtain peptide monomers under exceptionally mild reaction conditions. The homo and co-polypeptide bearing a reactive styrene moiety are prepared through the polycondensation of N-phenoxycarbonyl derivative of 4-vinylbenzyl-L-cysteine (NPC-Cys(VBn)) with the elimination of phenol and CO2 while varying the feed ratio to the primary amine initiator to give the corresponding polypeptides without any degradation of styrene moieties. The postpolymerization modification of styrene moiety is carried out by a radical addition or thiol-ene (photo) click reaction using 1,4-bis(3-mercaptobutylyloxy) butane, leading to the formation of a cross-linked polypeptide. The prepolymerization modification of NPC-Cys(VBn) by a click reaction with benzyl mercaptan as a model compound also demonstrates the side-chain functionalization to make a new monomer for polypeptide synthesis.