Université de Strasbourg, CNRS, Institut Charles Sadron UPR22, 23 rue du Loess, 67034, Strasbourg Cedex 2, France.
Aix Marseille Univ, CNRS, ICR UMR7273, 13397, Marseille, France.
Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7297-7301. doi: 10.1002/anie.201702384. Epub 2017 May 15.
A three-step post-polymerization modification method was developed for the design of digitally encoded poly(phosphodiester)s with controllable side groups. Sequence-defined precursors were synthesized, either manually on polystyrene resins or automatically on controlled pore glass supports, using two phosphoramidite monomers containing either terminal alkynes or triisopropylsilyl (TIPS) protected alkyne side groups. Afterwards, these polymers were modified by stepwise copper-catalyzed azide-alkyne cycloaddition (CuAAC). The terminal alkynes were first reacted with a model azide compound, and after removal of the TIPS groups, the remaining alkynes were reacted with another organic azide. This simple method allows for quantitative side-chain modification, thus opening up interesting avenues for the preparation of a wide variety of digital polymers.
开发了一种三步后聚合修饰方法，用于设计具有可控侧基的数字编码聚（磷酸二酯）。使用两种含有末端炔基或三异丙基硅基（TIPS）保护炔基侧基的磷酰胺单体，通过手动在聚苯乙烯树脂上或自动在可控孔玻璃载体上合成序列定义的前体。然后，通过逐步铜催化叠氮-炔环加成（CuAAC）对这些聚合物进行修饰。首先将末端炔基与模型叠氮化合物反应，然后去除 TIPS 基团，剩余的炔基与另一种有机叠氮化合物反应。这种简单的方法允许定量的侧链修饰，从而为制备各种数字聚合物开辟了有趣的途径。
