Synthesis and Topological Conversion of an 8-shaped Poly(THF) Having a Metathesis-Cleavable Unit at the Focal Position

A pair of 8-shaped poly(tetrahydrofuran)s, poly(THF)s, having a metathesis-cleavable olefinic unit of isomeric forms at the focal position, IIa and IIb, has been synthesized through an electrostatic self-assembly and covalent fixation (ESA-CF) process using a telechelic poly(THF) having N-phenylpyrrolidinium salt groups carrying a tetracarboxylate counteranion containing a trans-3-hexenyl group, as equilibrated isomeric forms of Ia and Ib. The subsequent metathesis cleavage reaction of the olefinic group in IIa and IIb has been conducted with a second generation Grubbs catalyst in the presence of ethyl vinyl ether. The polymer topology was thus converted from a dicyclic 8-shape into two simple loops having the two distinctive sizes consisting of one and two prepolymer units, IIIa and IIIb, respectively, corresponding to the linking mode of the two prepolymer segments on the pair of carboxylate groups at either the neighboring or the remote sites of the tetracarboxylate. Moreover, MALDI−TOF mass analysis h...