Folding Construction of a Pentacyclic Quadruply fused Polymer Topology with Tailored kyklo‐Telechelic Precursors

Abstract

A pentacyclic quadruply fused polymer topology has been constructed for the first time through alkyne-azide addition (click) and olefin metathesis (clip) reactions in conjunction with an electrostatic self-assembly and covalent fixation (ESA-CF) process. Thus, a spiro-type, tandem tetracyclic poly(tetrahydrofuran), poly(THF), precursor having two allyloxy groups at the opposite positions of the four ring units was prepared by the click-linking of one unit of an eight-shaped precursor having alkyne groups at the opposite positions with two units of a single-cyclic counterpart having an azide and an alkene group at the opposite positions. Both are obtainable through ESA-CF. The subsequent metathesis clip-folding of the tetracyclic precursor could afford a pentacyclic quadruply fused polymer product, of "shippo" form, in 19% yield.