通过点击环化和烯烃复分解夹合反应合成分子魅力手链。

Synthesis of a molecular charm bracelet via click cyclization and olefin metathesis clipping.

机构信息

The Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.

出版信息

J Am Chem Soc. 2010 Mar 17;132(10):3405-12. doi: 10.1021/ja9090337.

DOI:10.1021/ja9090337

PMID:20158251

Abstract

We describe the synthesis of a polycatenated cyclic polymer, a structure that resembles a molecular charm bracelet. Ruthenium-catalyzed ring-opening metathesis polymerization of an amino-containing cyclic olefin monomer in the presence of a chain transfer agent generated an alpha,omega-diazide functionalized polyamine. Cyclization of the resulting linear polyamine using pseudo-high-dilution copper-catalyzed click cyclization produced a cyclic polymer in 19% yield. The click reaction was then further employed to remove linear contaminants from the cyclic polymer using azide- and alkyne-functionalized scavenging resins, and the purified cyclic polymer product was characterized by gel permeation chromatography, (1)H NMR spectroscopy, and IR spectroscopy. Polymer hydrogenation and conversion to the corresponding polyammonium species enabled coordination and interlocking of diolefin polyether fragments around the cyclic polymer backbone using ruthenium-catalyzed ring-closing olefin metathesis to afford a molecular charm bracelet structure. This charm bracelet complex was characterized by (1)H NMR spectroscopy, and the catenated nature of the small rings was confirmed using two-dimensional diffusion-ordered NMR spectroscopy.

摘要

我们描述了一种多链式环状聚合物的合成方法，这种结构类似于分子手链。在链转移剂的存在下，含氨基的环状烯烃单体的钌催化开环复分解聚合生成了α,ω-叠氮功能化的多胺。所得线性多胺使用拟高稀释铜催化点击环化反应进行环化，以 19%的收率得到环状聚合物。然后，点击反应进一步用于使用叠氮化物和炔烃功能化的清除树脂从环状聚合物中去除线性污染物，并通过凝胶渗透色谱、（1）H NMR 光谱和 IR 光谱对纯化的环状聚合物产物进行表征。聚合物氢化和转化为相应的聚铵盐，使二烯烃聚醚片段能够在环状聚合物主链周围通过钌催化的闭环烯烃复分解进行配位和互锁，从而得到分子手链结构。该手链配合物通过（1）H NMR 光谱进行了表征，并使用二维扩散有序 NMR 光谱证实了小环的链式性质。