Photocontrolled Radical Polymerization from Hydridic C–H Bonds
Photocontrolled Radical Polymerization from Hydridic C–H Bonds
复制标题
氢 C–H 键的光控自由基聚合
DOI：
10.1021/jacs.0c00287
复制
发表时间：
2020
影响因子：
15
通讯作者：
Fors, Brett P.
中科院分区：
文献类型：
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作者：
Stache, Erin E.;Kottisch, Veronika;Fors, Brett P.
鉴于生物分子和聚合物主链中碳-氢键的普遍存在，从C-H键选择性接枝的光控聚合的发展代表了聚合物缀合的有力策略。这种方法将避免目前用于在聚合物链末端引入官能度的复杂合成途径的需要。在此基础上，我们开发了一种氢原子提取策略，允许使用二苯甲酮光催化剂，三硫代碳酸酯衍生的二硫化物和可见光选择性地从非线性C-H键进行受控聚合。我们从各种醚、烷烃、未活化的C-H键和醇进行聚合。我们的方法适合于光控，这对构建先进的大分子结构具有重要意义。最后，我们证明，我们可以接枝聚合物链可控地从聚（乙二醇）展示这种方法的潜在应用控制接枝从商品聚合物的C-H键。
Given the ubiquity of carbon–hydrogen bonds in biomolecules and polymer backbones, the development of a photocontrolled polymerization selectively grafting from a C–H bond represents a powerful strategy for polymer conjugation. This approach would circumvent the need for complex synthetic pathways currently used to introduce functionality at a polymer chain end. On this basis, we developed a hydrogen-atom abstraction strategy that allows for a controlled polymerization selectively from a hydridic C–H bond using a benzophenone photocatalyst, a trithiocarbonate-derived disulfide, and visible light. We performed the polymerization from a variety of ethers, alkanes, unactivated C–H bonds, and alcohols. Our method lends itself to photocontrol which has important implications for building advanced macromolecular architectures. Finally, we demonstrate that we can graft polymer chains controllably from poly(ethylene glycol) showcasing the potential application of this method for controlled grafting from C–H bonds of commodity polymers.