EaStCHEM, School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, EH9 3FJ, UK.
WestCHEM, School of Chemistry, University of Glasgow, Joseph Black Building, University Avenue, Glasgow, G12 8QQ, UK.
Angew Chem Int Ed Engl. 2018 Sep 24;57(39):12835-12839. doi: 10.1002/anie.201805113. Epub 2018 Jun 20.
Whereas complex stereoregular cyclic architectures are commonplace in biomacromolecules, they remain rare in synthetic polymer chemistry, thus limiting the potential to develop synthetic mimics or advanced materials for biomedical applications. Herein we disclose the formation of a stereocontrolled 1,4-linked six-membered cyclopolyether prepared by ring-closing metathesis (RCM). Ru-mediated RCM, with careful control of the catalyst, concentration, and temperature, selectively affords the six-membered-ring cyclopolymer. Under optimized reaction conditions, no metathetical degradation, macrocycle formation, or cross-linking was observed. Post-polymerization modification by dihydroxylation afforded a novel polymer family encompassing a poly(ethylene glycol) backbone and sugar-like functionalities ("PEGose"). This strategy also paves the way for using RCM as an efficient method to synthesize other stereocontrolled cyclopolymers.
虽然复杂的立体规整环状结构在生物大分子中很常见，但在合成聚合物化学中仍然很少见，因此限制了开发用于生物医学应用的合成模拟物或先进材料的潜力。本文中，我们揭示了通过闭环复分解（RCM）形成立体控制的 1,4-连接的六元环环聚醚。通过 Ru 介导的 RCM，并仔细控制催化剂、浓度和温度，可以选择性地得到六元环环聚合物。在优化的反应条件下，没有观察到复分解降解、大环形成或交联。聚合后通过二羟基化进行的修饰提供了一种新型聚合物家族，包括聚（乙二醇）主链和糖样官能团（“PEGose”）。该策略还为使用 RCM 作为合成其他立体控制环聚合物的有效方法铺平了道路。
