C−H Functionalization and Allylic Amination for Post‐Polymerization Modification of Polynorbornenes
C−H Functionalization and Allylic Amination for Post‐Polymerization Modification of Polynorbornenes
复制标题
用于聚降冰片烯聚合后改性的 C–H 官能化和烯丙基胺化
DOI：
10.1002/anie.202303174
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Boydston, Andrew J.
中科院分区：
文献类型：
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作者：
Gitter, Sean R.;Teh, Wei Pin;Yang, Xuejin;Dohoda, Alexander F.;Michael, Forrest E.;Boydston, Andrew J.
通过直接C-H官能化进行聚合后改性（PPM）是一种将聚合物原料转化为增值产品的强大合成策略。我们发现，无金属，硒催化的烯丙基C-H胺化提供了一种有效的方法PPM的聚异丁烯（PNB）通过开环易位聚合。与烯丙基胺化机理固有的是，PNB上的PPM保留了沿着聚合物主链的烯烃官能团，同时还避免了双键的换位。使用一系列芳基磺酰胺的胺化导致对官能化程度的良好控制，获得一系列官能度，以及所得聚合物的可调热性能。
Post‐polymerization modification (PPM) via direct C−H functionalization is a powerful synthetic strategy to convert polymer feed‐stocks into value‐added products. We found that a metal‐free, Se‐catalyzed allylic C−H amination provided an efficient method for PPM of polynorbornenes (PNBs) produced via ring‐opening metathesis polymerization. Inherent to the mechanism of the allylic amination, PPM on PNBs preserved the alkene functional groups along the polymer backbone, while also avoiding transposition of the double bonds. Amination using a series of aryl sulfonamides led to good control over the degree of functionalization, access to a range of functionalities, and tunable thermal properties from the resulting polymers.