Complex polymer topologies built from tailored multifunctional cyclic polymers

Complex polymer structures, including a spiro tricyclic and first generation dendritic structures, were constructed from cyclic polymer building blocks. We described a new method to produce monocyclic polymers with hydroxyl groups equally spaced along the polymer backbone. A key synthetic feature was carrying out the CuAAC reaction of telechelic polymer chains in the presence of a bromine group through modulating the Cu(I) activity toward the “click” reaction over radical formation. This allowed the precise control over the location of the OH groups. Azidation of the bromine groups and cyclization using a modified feed approach resulted in multifunctional monocyclics in high amounts and high purity of greater than 99% after fractionation. Conversion of the OH groups to either azide or alkyne functionality produced the central core macromolecule from which the more complex topologies were built. All four complex topologies, including a spiro tricyclic, and dendritic structures consisting of a G1 pentacycli...

[1]  R. Álvarez,et al.  Total synthesis of enantiopure pyrrhoxanthin: alternative methods for the stereoselective preparation of 4-alkylidenebutenolides. , 2013, Chemistry.

[2]  Zhongfan Jia,et al.  Cyclic polystyrene topologies via RAFT and CuAAC , 2012 .

[3]  Andreas F. M. Kilbinger,et al.  ROMP Copolymers for Orthogonal Click Functionalizations , 2012 .

[4]  Xinghe Fan,et al.  Effects of Dendron Generation and Salt Concentration on Phase Structures of Dendritic–Linear Block Copolymers with a Semirigid Dendron Containing PEG Tails , 2012 .

[5]  Zhongfan Jia,et al.  Construction of a 3-Miktoarm Star from Cyclic Polymers. , 2012, ACS macro letters.

[6]  Zhongfan Jia,et al.  Cyclic polymers: Methods and strategies , 2012 .

[7]  S. Perrier,et al.  Dendritic and Hyperbranched Polymers from Macromolecular Units: Elegant Approaches to the Synthesis of Functional Polymers , 2011 .

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

[9]  Eun Ji Shin,et al.  Zwitterionic copolymerization: synthesis of cyclic gradient copolymers. , 2011, Angewandte Chemie.

[10]  Zhongfan Jia,et al.  Modulating Two Copper(I)-Catalyzed Orthogonal “Click” Reactions for the One-Pot Synthesis of Highly Branched Polymer Architectures at 25 °C , 2011 .

[11]  Kecheng Zhang,et al.  Universal cyclic polymer templates. , 2011, Journal of the American Chemical Society.

[12]  Zhongfan Jia,et al.  Directing the pathway of orthogonal 'click' reactions by modulating copper-catalytic activity. , 2011, Chemical communications.

[13]  Eun Ji Shin,et al.  Crystallization of Cyclic Polymers: Synthesis and Crystallization Behavior of High Molecular Weight Cyclic Poly(ε-caprolactone)s , 2011 .

[14]  G. Tew,et al.  Gels based on cyclic polymers. , 2011, Journal of the American Chemical Society.

[15]  Masahiro Fujita,et al.  DNA-functionalized thermoresponsive bioconjugates synthesized via ATRP and click chemistry , 2011 .

[16]  M. Monteiro,et al.  Various polystyrene topologies built from tailored cyclic polystyrene via CuAAC reactions. , 2010, Chemical communications.

[17]  M. Monteiro,et al.  Kinetic simulations for cyclization of α,ω‐telechelic polymers , 2010 .

[18]  M. Monteiro,et al.  Ultrafast and Reversible Multiblock Formation by the SET-Nitroxide Radical Coupling Reaction , 2010 .

[19]  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.

[20]  M. Monteiro,et al.  Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr , 2010 .

[21]  M. Monteiro,et al.  Strategy for Rapid and High-Purity Monocyclic Polymers by CuAAC “Click” Reactions , 2010 .

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

[23]  Sixun Zheng,et al.  Reaction-induced microphase separation in epoxy resin containing polystyrene-block-poly(ethylene oxide) alternating multiblock copolymer , 2009 .

[24]  R. Hoogenboom,et al.  Star-Shaped Polyacrylates: Highly Functionalized Architectures via CuAAC Click Conjugation. , 2009, Macromolecular rapid communications.

[25]  Paulo J. Costa,et al.  Sulfate anion templated synthesis of a triply interlocked capsule. , 2009, Chemical communications.

[26]  M. Monteiro,et al.  Rapid, Selective, and Reversible Nitroxide Radical Coupling (NRC) Reactions at Ambient Temperature , 2009 .

[27]  Scott M. Grayson,et al.  Synthetic approaches for the preparation of cyclic polymers. , 2009, Chemical Society reviews.

[28]  F. Du,et al.  Preparation of Tadpole-Shaped Amphiphilic Cyclic PS-b-linear PEO via ATRP and Click Chemistry , 2009 .

[29]  Scott M. Grayson,et al.  Efficient Preparation of Cyclic Poly(methyl acrylate)-block-poly(styrene) by Combination of Atom Transfer Radical Polymerization and Click Cyclization , 2008 .

[30]  Carl N. Urbani,et al.  Divergent Synthesis and Self-Assembly of Amphiphilic Polymeric Dendrons with Selective Degradable Linkages , 2008 .

[31]  Craig A. Bell,et al.  Convergent Synthesis of Second Generation AB-Type Miktoarm Dendrimers Using ``Click'' Chemistry Catalyzed by Copper Wire , 2008 .

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

[33]  Jean-François Lutz,et al.  1,3-dipolar cycloadditions of azides and alkynes: a universal ligation tool in polymer and materials science. , 2007, Angewandte Chemie.

[34]  H. Börner,et al.  Combining ATRP and “Click” Chemistry: a Promising Platform toward Functional Biocompatible Polymers and Polymer Bioconjugates , 2006 .

[35]  Michael J Monteiro,et al.  Synthesis of 3-miktoarm stars and 1st generation mikto dendritic copolymers by "living" radical polymerization and "click" chemistry. , 2006, Journal of the American Chemical Society.

[36]  Scott M. Grayson,et al.  An efficient route to well-defined macrocyclic polymers via "click" cyclization. , 2006, Journal of the American Chemical Society.

[37]  Y. Tezuka,et al.  Designing 8-Shaped Polymer Topology by Metathesis Condensation with Cyclic Poly(THF) Precursors Having Allyl Groups , 2003 .

[38]  T. McLeish.  Polymers Without Beginning or End , 2002, Science.

[39]  R. Grubbs,et al.  An "Endless" Route to Cyclic Polymers , 2002, Science.

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

[41]  H. Oike,et al.  Self‐Assembly and Covalent Fixation for Topological Polymer Chemistry , 2001 .

[42]  M. G. Finn,et al.  Click Chemistry: Diverse Chemical Function from a Few Good Reactions. , 2001, Angewandte Chemie.

[43]  Stephen E. Cabaniss,et al.  A log-normal distribution model for the molecular weight of aquatic fulvic acids , 2000 .

[44]  Obukhov,et al.  Dynamics of a ring polymer in a gel. , 1994, Physical review letters.

[45]  J. Roovers,et al.  Synthesis of high molecular weight ring polystyrenes , 1983 .

[46]  H. Höcker,et al.  Synthesis and Investigation of Macrocyclic Polystyrene , 1980 .

[47]  Homer Jacobson,et al.  Intramolecular Reaction in Polycondensations. I. The Theory of Linear Systems , 1950 .