Fast and selective organocatalytic ring-opening polymerization by fluorinated alcohol without a cocatalyst
Fast and selective organocatalytic ring-opening polymerization by fluorinated alcohol without a cocatalyst
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无助催化剂的氟化醇快速选择性有机催化开环聚合
DOI：
10.1038/s41467-019-11524-y
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发表时间：
2019-08-09
影响因子：
16.6
通讯作者：
Hadjichristidis, Nikos
中科院分区：
文献类型：
--
作者：
Zhao, Wei;Lv, Yanfeng;Hadjichristidis, Nikos
有机催化是催化学的一个重要分支，用于各种有机转化和材料制备。有机催化剂促进的聚合反应可以生产出无金属残留的聚合物材料，为生物医学应用、微电子器件和食品包装等高价值和敏感领域提供了极具吸引力的材料。本文介绍了一种以氟化醇为催化剂的α-氨基酸-N-羧酸酐（NCA）开环聚合（ROP）合成多肽的催化体系，实现了无助催化剂、无金属、高速率和高选择性。在聚合过程中，氟化醇催化剂与引发剂、单体和增长的聚合物链形成多个动态氢键。这些协同氢键相互作用活化NCA单体，同时保护过活性引发剂/增长聚合物链端，这为整个聚合提供了高活性和高选择性。机理研究表明，含氟醇的催化模式为单组分-多功能模式。这一发现提供了一种无金属和快速的方法来获得明确定义的多肽。
Organocatalysis is an important branch of catalysis for various organic transformations and materials preparation. Polymerizations promoted by organic catalysts can produce polymeric materials without any metallic residues, providing charming materials for high-value and sensitive domains such as biomedical applications, microelectronic devices and food packaging. Herein, we describe a fluorinated alcohol based catalytic system for polypeptide synthesis via catalytic ring-opening polymerization (ROP) ofα-amino acidN-carboxyanhydride (NCA), fulfilling cocatalyst free, metal free, high rate and high selectivity. During polymerization, the fluorinated alcohol catalyst forms multiple dynamic hydrogen bonds with the initiator, monomer and propagating polymer chain. These cooperative hydrogen bonding interactions activate the NCA monomers and simultaneously protect the overactive initiator/propagating polymer chain-ends, which offers the whole polymerization with high activity and selectivity. Mechanistic studies indicate a monocomponent-multifunctional catalytic mode of fluorinated alcohol. This finding provides a metal free and fast approach to access well-defined polypeptides.