Concise Click/ESA-CF Synthesis of Periodically-Positioned Trifunctional kyklo-Telechelic Poly(THF)s

A concise two-step click/ESA-CF process has been developed to prepare a kyklo-telechelic poly(tetrahydrofuran), poly(THF), having three functional groups at the constant intervals. Thus, a key linear precursor (I), having N-phenylpyrrolidinium salt groups at the chain ends and having two hydroxyl groups at the prescribed inner positions, has been prepared through the alkyne–azide addition (click) reaction using one unit of a linear telechelic poly(THF) having a pair of an alkyne and a hydroxyl groups (1) and two units of a linear asymmetric telechelic poly(THF) having an azide and an N-phenylpyrrolidinium salt group (2). The subsequent polymer cyclization by means of an electrostatic self-assembly and covalent fixation (ESA-CF) process, by employing a dicarboxylate counteranion having an additional alkyne group (3) to I, could produce a trifunctional kyklo-telechelic poly(THF) (II), having two hydroxyl and one alkyne groups positioned at the constant intervals along the ring polymer backbone. The subseque...

[1]  Takuya Yamamoto,et al.  Cyclic polymers revealing topology effects upon self-assemblies, dynamics and responses. , 2015, Soft matter.

[2]  Takuya Yamamoto,et al.  Folding Construction of a Pentacyclic Quadruply fused Polymer Topology with Tailored kyklo-Telechelic Precursors. , 2015, Angewandte Chemie.

[3]  Y. S. Ko,et al.  Construction of Double-Eight and Double-Trefoil Polymer Topologies with Core-Clickable kyklo-Telechelic Precursors , 2014 .

[4]  Zhongfan Jia,et al.  Complex polymer topologies built from tailored multifunctional cyclic polymers , 2014 .

[5]  S. Grayson,et al.  Special issue ‘Cyclic polymers: New developments’ , 2014 .

[6]  Takuya Yamamoto,et al.  Folding Construction of Doubly Fused Tricyclic, β- and γ‑Graph Polymer Topologies with kyklo-Telechelic Precursors Obtained through an Orthogonal Click/ESA-CF Protocol , 2013 .

[7]  Joshua A. Kaitz,et al.  End group characterization of poly(phthalaldehyde): surprising discovery of a reversible, cationic macrocyclization mechanism. , 2013, Journal of the American Chemical Society.

[8]  R. Waymouth,et al.  Zwitterionic ring-opening polymerization for the synthesis of high molecular weight cyclic polymers. , 2013, Accounts of chemical research.

[9]  M. Ouchi,et al.  Ring-Expansion Living Cationic Polymerization via Reversible Activation of a Hemiacetal Ester Bond. , 2013, ACS macro letters.

[10]  H. Hurley,et al.  Lactide Cyclopolymerization Kinetics, X-ray Structure, and Solution Dynamics of (tBu-SalAmEE)Al and a Cautionary Tale Of Polymetalate Formation , 2013 .

[11]  Zhongfan Jia,et al.  Synthesis of cyclic polymers via ring closure , 2013 .

[12]  Y. Tezuka.  Topological Polymer Chemistry:Progress of Cyclic Polymers in Syntheses, Properties and Functions , 2012 .

[13]  Y. Tezuka.  Topological polymer chemistry for designing multicyclic macromolecular architectures , 2012 .

[14]  Takuya Yamamoto,et al.  A programmed polymer folding: click and clip construction of doubly fused tricyclic and triply fused tetracyclic polymer topologies. , 2011, Journal of the American Chemical Society.

[15]  Takuya Yamamoto,et al.  Topological polymer chemistry: a cyclic approach toward novel polymer properties and functions , 2011 .

[16]  Qi Meng,et al.  Effective click construction of bridged- and spiro-multicyclic polymer topologies with tailored cyclic prepolymers (kyklo-telechelics). , 2010, Journal of the American Chemical Society.

[17]  H. Kricheldorf.  Cyclic polymers: Synthetic strategies and physical properties , 2010 .

[18]  R. Grubbs,et al.  Ring-expansion metathesis polymerization: catalyst-dependent polymerization profiles. , 2009, Journal of the American Chemical Society.

[19]  J. Fraser Stoddart,et al.  A redox-switchable alpha-cyclodextrin-based [2]rotaxane. , 2008, Journal of the American Chemical Society.

[20]  K. Endo.  Synthesis and Properties of Cyclic Polymers , 2008 .

[21]  Rachel K. O'Reilly,et al.  Dendrimers Clicked Together Divergently , 2005 .

[22]  Y. Tezuka,et al.  Construction of Polymeric δ-Graph: A Doubly Fused Tricyclic Topology , 2005 .

[23]  H. Oike,et al.  Topological polymer chemistry: systematic classification of nonlinear polymer topologies. , 2001, Journal of the American Chemical Society.

[24]  H. Oike,et al.  Designing Unusual Polymer Topologies by Electrostatic Self-Assembly and Covalent Fixation , 2000 .

[25]  J. Katzenellenbogen,et al.  Synthesis of a tetrafluoro-substituted aryl azide and its protio analog as photoaffinity labeling reagents for the estrogen receptor , 1991 .

[26]  A. Cunliffe,et al.  Reaction to effect the transformation of anionic polymerization into cationic polymerization: 3. Analysis of block copolymer formation by gel permeation chromatography , 1977 .