Liquid-Phase Synthesis of Block Copolymers Containing Sequence-Ordered Segments

Liquid-Phase Synthesis of Block Copolymers Containing Sequence-Ordered Segments
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DOI:
10.1021/ja903635y
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发表时间:
2009-07-08
影响因子:
15
通讯作者:
Lutz, Jean-Francois
Lutz, Jean-Francois
中科院分区:
化学1区
文献类型:
--
作者:
Pfeifer, Sebastian;Zarafshani, Zoya;Lutz, Jean-Francois

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单分散的序列限定的低聚物已在溶液中合成的保护基团的情况下。这些结构已准备逐步使用两个连续的化学选择性反应:1,3-偶极环加成的末端炔和叠氮化物和酰胺化的羧酸与伯胺。这些低聚物可以有效地构建在传统的固体载体(商业Wang树脂)或通过原子转移自由基聚合合成的定制可溶性聚苯乙烯载体上。后一种方法被认为是非常通用的。事实上,明确定义的可溶性大分子载体不仅允许合成和裂解确定的低聚物(即,牺牲载体),而且制备含有序列限定的链段的不可裂解的嵌段共聚物。
Monodisperse sequence-defined oligomers have been synthesized in solution in the absence of protecting groups. These structures have been prepared stepwise using two consecutive chemoselective reactions: 1,3-dipolar cycloaddition of terminal alkynes and azides and amidification of carboxylic acids with primary amines. These oligomers were efficiently constructed on either a conventional solid support (commercial Wang resin) or tailor-made soluble polystyrene supports synthesized by atom-transfer radical polymerization. The latter approach was found to be very versatile. Indeed, well-defined soluble macromolecular supports allowed not only the synthesis and cleavage of defined oligomers (i.e., sacrificial support) but also the preparation of noncleavable block Copolymers containing sequence-defined segments.