School of Chemistry and Biochemistry , Georgia Institute of Technology , 901 Atlantic Drive NW , Atlanta , Georgia 30332 , United States.
J Am Chem Soc. 2018 Sep 26;140(38):12181-12188. doi: 10.1021/jacs.8b07315. Epub 2018 Sep 11.
The covalent coupling of complex macromolecules is a modern challenge in both chemistry and biology. The development of efficient and chemoselective methods for polymer coupling and functionalization are increasingly important for designing new advanced materials and interfacing with biochemical systems. Herein, we present a new strategy to directly conjugate living polymers prepared using ring-opening metathesis polymerization (ROMP) to both small molecules and synthetic macromolecules. Central to this methodology is a terminal alkyne that serves as a directing group to promote a rapid, intramolecular reaction with an otherwise unreactive olefin. This highly chemoselective relay conjugation is compatible with a range of monomer families and uses a bench-stable enyne motif that can be easily introduced to functional targets. The rapid rate of the conjugation reaction paves the way for greatly streamlined construction of complex macromolecular systems derived from metathesis polymerization techniques without the need for specialized equipment.
复杂大分子的共价偶联是化学和生物学领域的一个现代挑战。开发高效和选择性的聚合物偶联和功能化方法对于设计新型先进材料和与生化系统接口越来越重要。在此，我们提出了一种新策略，可直接将使用开环复分解聚合（ROMP）制备的活性聚合物与小分子和合成大分子偶联。该方法的核心是一个末端炔烃，它作为导向基团，促进与否则不反应的烯烃的快速分子内反应。这种高化学选择性的接力偶联与一系列单体家族兼容，并使用稳定的烯炔基序，可以轻松引入功能化目标。偶联反应的快速速率为简化复杂大分子系统的构建铺平了道路，这些系统源自不需要特殊设备的复分解聚合技术。
