Sequential Triple "Click" Approach toward Polyhedral Oligomeric Silsesquioxane-Based Multiheaded and Multitailed Giant Surfactants.
Sequential Triple "Click" Approach toward Polyhedral Oligomeric Silsesquioxane-Based Multiheaded and Multitailed Giant Surfactants.
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DOI：
10.1021/mz4002723
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发表时间：
2013-07
影响因子：
5.8
通讯作者：
Hao Su;Jukuan Zheng;Zhao Wang;Feiyue Lin;Xueyan Feng;Xue-hui Dong;M. Becker;Stephen Z. D. Cheng
中科院分区：
文献类型：
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作者：
Hao Su;Jukuan Zheng;Zhao Wang;Feiyue Lin;Xueyan Feng;Xue-hui Dong;M. Becker;Stephen Z. D. Cheng
本文报道了一种连续的三重“点击”化学方法，用于精确合成功能性多面体低聚倍半硅氧烷（POSS）基多头和多尾巨型表面活性剂。具有两个不同反应性的炔基的乙烯基POSS基异双官能结构单元被用作坚固且强大的“可点击”前体，用于随时获得具有复杂结构的各种POSS基形状两亲物。该合成方法包括依次进行应变促进的叠氮化合物-炔环加成反应（SPAAC）、铜催化的叠氮化合物-炔环加成反应（CuAAC）和硫醇-烯“点击”偶联反应（TECC）。具体地，发现第一SPAAC反应是高度选择性的，没有来自前体中的乙烯基和末端炔的并发症。该方法扩展了连续“点击”方法的工具箱，并拓宽了合成可用的巨型表面活性剂的范围，以进一步研究结构-性能关系。
This letter reports a sequential triple "click" chemistry method for the precise synthesis of functional polyhedral oligomeric silsesquioxane (POSS)-based multiheaded and multitailed giant surfactants. A vinyl POSS-based heterobifunctional building block possessing two alkyne groups of distinct reactivity was used as a robust and powerful "clickable" precursor for ready access to a variety of POSS-based shape amphiphiles with complex architectures. The synthetic approach involves sequentially performed strain-promoted azide-alkyne cycloaddition (SPAAC), copper-catalyzed azide-alkyne cycloaddition (CuAAC), and thiol-ene "click" coupling (TECC). Specifically, the first SPAAC reaction was found to be highly selective with no complications from the vinyl groups and terminal alkynes in the precursor. The method expands the toolbox of sequential "click" approaches and broadens the scope of synthetically available giant surfactants for further study on structure-property relationships.