Abstract

AbstractA 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.

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