Synthesis of Carbohydrate-Grafted Glycopolymers Using a Catalyst-Free, Perfluoroarylazide-Mediated Fast Staudinger Reaction
Synthesis of Carbohydrate-Grafted Glycopolymers Using a Catalyst-Free, Perfluoroarylazide-Mediated Fast Staudinger Reaction
复制标题
DOI：
10.3390/molecules24010157
复制
发表时间：
2019-01
期刊：
影响因子：
4.6
通讯作者：
William Ndugire;Bin Wu;Mingdi Yan
中科院分区：
文献类型：
--
作者：
William Ndugire;Bin Wu;Mingdi Yan
糖共聚物在研究糖-凝集素相互作用、作为药物载体和调节与蛋白质的相互作用方面具有越来越重要的作用。这些糖共聚物的合成仍然是一项具有挑战性和严谨性的工作。在这方面，高效的点击反应，铜(I)催化的炔叠氮环加成反应，不仅因为它的效率，而且因为它对加成的碳水化合物基团的耐受性而被广泛应用。然而，这种方法的一个显著缺点是使用的重金属催化剂很难完全去除，最终对生物系统有害。在这项工作中，我们提出了利用温和的、无催化剂的全氟苯叠氮(PFPA)介导的Staudinger反应来合成碳水化合物接枝糖共聚物。采用这种方法，在室温下，通过在二甲基亚砜中搅拌PFAA功能化的聚乳酸，将甘露糖(MAN)和麦芽七糖(MH)接枝到可生物降解的聚乳酸(PLA)上。用~1H-核磁共振、~(19)F-核磁共振、~(31)P-核磁共振和傅立叶变换红外光谱对其进行了表征。
Glycopolymers have gained increasing importance in investigating glycan-lectin interactions, as drug delivery vehicles and in modulating interactions with proteins. The synthesis of these glycopolymers is still a challenging and rigorous exercise. In this regard, the highly efficient click reaction, copper (I)-catalyzed alkyne-azide cycloaddition, has been widely applied not only for its efficiency but also for its tolerance of the appended carbohydrate groups. However, a significant drawback of this method is the use of the heavy metal catalyst which is difficult to remove completely, and ultimately toxic to biological systems. In this work, we present the synthesis of carbohydrate-grafted glycopolymers utilizing a mild and catalyst-free perfluorophenyl azide (PFPA)-mediated Staudinger reaction. Using this strategy, mannose (Man) and maltoheptaose (MH) were grafted onto the biodegradable poly(lactic acid) (PLA) by stirring a PFAA-functionalized PLA with a phosphine-derivatized Man or MH in DMSO at room temperature within an hour. The glycopolymers were characterized by 1H-NMR, 19F-NMR, 31P-NMR and FTIR.