title: A programmed polymer folding: click and clip construction of doubly fused tricyclic and triply fused tetracyclic polymer topologies.
abstract: A tandem alkyne-azide addition, i.e., click, and an olefin metathesis condensation, i.e., clip, reactions in conjunction with an electrostatic self-assembly and covalent fixation (ESA-CF) process, have been demonstrated as effective means to produce constructions of programmed folding of polymers having doubly fused tricyclic and triply fused tetracyclic topologies. Thus, a series of cyclic poly(tetrahydrofuran), poly(THF), precursors having an allyloxy group and an alkyne group (Ia), an allyloxy group and an azide group (Ib), and two alkyne groups (Ic) at the opposite positions was prepared by means of the ESA-CF method. The subsequent click reactions of Ia with a linear telechelic poly(THF) precursor having azide end groups (Id) and of Ib with Ic afforded a bridged dicyclic polymer (IIa) and a tandem spiro tricyclic precursor (IIb), respectively, both having two allyloxy groups at the opposite positions of the ring units. Finally, the intramolecular metathesis condensation reaction of IIa and of IIb in the presence of a Grubbs catalyst was performed to construct effectively a doubly fused tricyclic and a triply fused tetracyclic polymer topologies (III and IV), respectively.
authors.affiliation: Department of Organic and Polymeric Materials, Tokyo Institute of Technology, O-okayama, Tokyo 152-8552, Japan.
authors.forename: Naoto
authors.initials: N
authors.lastname: Sugai
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Heguri
authors.forename: Takuya
authors.initials: T
authors.lastname: Yamamoto
authors.forename: Yasuyuki
authors.initials: Y
authors.lastname: Tezuka
mesh_terms: D000475:Alkenes / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D001386:Azides / Q000737:chemistry*; D003500:Cyclization; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D011108:Polymers / Q000737:chemistry*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D055672:Static Electricity
chemical_list: D000475:Alkenes; D000480:Alkynes; D001386:Azides; D011108:Polymers