Synthesis of dendritic macromolecules through divergent iterative thio‐bromo “Click” chemistry and SET‐LRP

The development of a novel nucleophilic thio-bromo “Click” reaction, specifically base-mediated thioetherification of thioglycerol with α-bromoesters was reported in an earlier article. The combination of this thio-bromo click reaction with subsequent acylation with 2-bromopropionyl bromide provides an iterative two-step divergent growth approach to the synthesis of a new class of poly(thioglycerol-2- propionate) (PTP) dendrimers. In this article, the addition of a third step, the single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA), was shown to provides access to a three-step “branch” and “grow” divergent approach to dendritic macromolecules wherein poly(methyl acrylate) (PMA) connects the branching subunits. This facile methodology can provide a diversity of dendritic macromolecular topologies and will ultimately provide the means to the development of self-organizable dendritic macromolecules. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3940–3948, 2009

[1]  J. N. Lowe,et al.  Synthesis, structural analysis, and visualization of a library of dendronized polyphenylacetylenes. , 2006, Chemistry.

[2]  V. Percec,et al.  Implications of monomer and initiator structure on the dissociative electron-transfer step of SET-LRP , 2008 .

[3]  V. Percec,et al.  Rational Design of the First Nonspherical Dendrimer Which Displays Calamitic Nematic and Smectic Thermotropic Liquid Crystalline Phases , 1995 .

[4]  V. Percec,et al.  Spherical Supramolecular Minidendrimers Self-Organized in an “Inverse Micellar”-like Thermotropic Body-Centered Cubic Liquid Crystalline Phase , 2000 .

[5]  R. Huisgen.  1,3-Dipolar Cycloadditions. Past and Future† , 1963 .

[6]  E. Chaikof,et al.  Synthesis of Water-Soluble Star-Block and Dendrimer-like Copolymers Based on Poly(ethylene oxide) and Poly(acrylic acid) , 2003 .

[7]  V. Percec,et al.  SET‐LRP of acrylates in the presence of radical inhibitors , 2008 .

[8]  V. Percec,et al.  Alkyl chloride initiators for SET‐LRP of methyl acrylate , 2008 .

[9]  V. Percec,et al.  Expanding the structural diversity of self-assembling dendrons and supramolecular dendrimers via complex building blocks. , 2007, Journal of the American Chemical Society.

[10]  D. Taton,et al.  Synthesis and Surface Properties of Amphiphilic Star-Shaped and Dendrimer-like Copolymers Based on Polystyrene Core and Poly(ethylene oxide) Corona , 2003 .

[11]  Carl N. Urbani,et al.  Synthesis of linear and 4‐arm star block copolymers of poly(methyl acrylate‐b‐solketal acrylate) by SET‐LRP at 25 °C , 2008 .

[12]  Goran Ungar,et al.  Giant Supramolecular Liquid Crystal Lattice , 2003, Science.

[13]  V. Percec,et al.  Toward self‐assembling dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible terminator multifunctional initiator , 2004 .

[14]  V. Percec,et al.  Synthesis of dendrimers through divergent iterative thio-bromo “Click” chemistry , 2009 .

[15]  V. Percec,et al.  Kinetic simulation of single electron transfer–living radical polymerization of methyl acrylate at 25 °C , 2007 .

[16]  V. Percec,et al.  Effect of Temperature on the Supramolecular Tubular Structure in Oriented Fibers of a Poly(methacrylate) with Tapered Side Groups , 1995 .

[17]  Virgil Percec,et al.  Synthesis and Structural Analysis of Two Constitutional Isomeric Libraries of AB2-Based Monodendrons and Supramolecular Dendrimers , 2001 .

[18]  V. Percec,et al.  Dramatic stabilization of a hexagonal columnar mesophase generated from supramolecular and macromolecular columns by the semifluorination of the alkyl groups of their tapered building blocks , 1995 .

[19]  V. Percec,et al.  Principles of self-assembly of helical pores from dendritic dipeptides. , 2006, Proceedings of the National Academy of Sciences of the United States of America.

[20]  Craig A. Bell,et al.  Self-Assembly of Amphiphilic Polymeric Dendrimers Synthesized with Selective Degradable Linkages , 2008 .

[21]  V. Percec,et al.  Rate Enhancement by Carboxylate Salts in the CuCl, Cu2O, and Cu(0) Catalyzed “Living” Radical Polymerization of Butyl Methacrylate Initiated with Sulfonyl Chlorides , 1998 .

[22]  V. Percec,et al.  A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP , 2007 .

[23]  D. Taton,et al.  Stars and dendrimer‐like architectures by the divergent method using controlled radical polymerization , 2001 .

[24]  Stephen Z. D. Cheng,et al.  VISUALIZABLE CYLINDRICAL MACROMOLECULES WITH CONTROLLED STIFFNESS FROM BACKBONES CONTAINING LIBRARIES OF SELF-ASSEMBLING DENDRITIC SIDE GROUPS , 1998 .

[25]  V. Percec,et al.  Nanomechanical function from self-organizable dendronized helical polyphenylacetylenes. , 2008, Journal of the American Chemical Society.

[26]  Yongming Chen,et al.  Divergent synthesis of dendrimer‐like macromolecules through a combination of atom transfer radical polymerization and click reaction , 2007 .

[27]  K. D. Singer,et al.  Self-organization of supramolecular helical dendrimers into complex electronic materials , 2002, Nature.

[28]  Scott R White,et al.  Mechanophore-linked addition polymers. , 2007, Journal of the American Chemical Society.

[29]  M. Glodde,et al.  Exploring and expanding the structural diversity of self-assembling dendrons through combinations of AB, constitutional isomeric AB2, and AB3 biphenyl-4-methyl ether building blocks. , 2006, Chemistry.

[30]  W. Ford,et al.  Branched poly(styrene-b-tert-butyl acrylate) and poly(styrene-b-acrylic acid) by ATRP from a dendritic poly(propylene imine)(NH2)64core , 2007 .

[31]  V. Percec,et al.  Self-assembly of taper-shaped monoesters of oligo(ethylene oxide) with 3,4,5-tris(n-dodecan-1-yloxy)benzoic acid and of their polymethacrylates into tubular supramolecular architectures displaying a columnar hexagonal mesophase , 1993 .

[32]  M. Ciampolini,et al.  Five-Coordinated High-Spin Complexes of Bivalent Cobalt, Nickel, andCopper with Tris(2-dimethylaminoethyl)amine , 1966 .

[33]  Yves Gnanou,et al.  Amphiphilic Stars and Dendrimer-Like Architectures Based on Poly(Ethylene Oxide) and Polystyrene , 2000 .

[34]  V. Percec,et al.  A comparative analysis of SET‐LRP of MA in solvents mediating different degrees of disproportionation of Cu(I)Br , 2008 .

[35]  S. D. Hudson,et al.  Self-assembly of amphiphilic dendritic dipeptides into helical pores , 2004, Nature.

[36]  J. Hedrick,et al.  Dendrimer-like Star Polymers , 1998 .

[37]  R. B. Grubbs,et al.  Synthesis of functional aromatic multisulfonyl chlorides and their masked precursors. , 2001, The Journal of organic chemistry.

[38]  R. B. Grubbs,et al.  Designing functional aromatic multisulfonyl chloride initiators for complex organic synthesis by living radical polymerization , 2000 .

[39]  T. Bera,et al.  Accelerated iterative strategy for the divergent synthesis of dendritic macromolecules using a combination of living radical polymerization and an irreversible terminator multifunctional initiator , 2005 .

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

[41]  V. Percec,et al.  Fluorophobic Effect Induces the Self-Assembly of Semifluorinated Tapered Monodendrons Containing Crown Ethers into Supramolecular Columnar Dendrimers Which Exhibit a Homeotropic Hexagonal Columnar Liquid Crystalline Phase , 1996 .

[42]  V. Percec,et al.  Living radical polymerization of styrene initiated by arenesulfonyl chlorides and CuI(bpy)nCl , 1995 .

[43]  V. Percec,et al.  Living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by nascent Cu0/tris(2‐aminoethyl)amine or polyethyleneimine in water at 25 °C proceeds by a new competing pathways mechanism , 2003 .

[44]  T. Bera,et al.  CuI and CuII salts of group VIA elements as catalysts for living radical polymerization initiated with sulfonyl chlorides , 2000 .

[45]  C. Ahn,et al.  Self-Encapsulation, Acceleration and Control in the Radical Polymerization of Monodendritic Monomers via Self-Assembly , 1997 .

[46]  V. Percec,et al.  Supramolecular Tubular Structures of a Polymethacrylate with Tapered Side Groups in Aligned Hexagonal Phases , 1994 .

[47]  V. Percec,et al.  Self-regulated phase transfer of Cu2O/bpy, Cu(0)/bpy, and Cu2O/Cu(0)bpy catalyzed living radical polymerization initiated with sulfonyl chlorides , 1998 .

[48]  C. Ahn,et al.  Controlling polymer shape through the self-assembly of dendritic side-groups , 1998, Nature.

[49]  V. Percec,et al.  The influence of the complexation of sodium and lithium triflate on the self-assembly of tubular-supramolecular architectures displaying a columnar mesophase based on taper-shaped monoesters of oligoethylene oxide with 3,4,5-tris[p-(n-dodecan-1-yloxy)benzyloxy]benzoic acid and of their polymethacryl , 1993 .

[50]  M. R. Imam,et al.  Self-assembly of dendronized triphenylenes into helical pyramidal columns and chiral spheres. , 2009, Journal of the American Chemical Society.

[51]  V. Percec,et al.  Surface-Dependent Kinetics of Cu(0)-Wire-Catalyzed Single-Electron Transfer Living Radical Polymerization of Methyl Acrylate in DMSO at 25 °C , 2009 .

[52]  D. Schlueter,et al.  Mechanistic Investigations on the Formation of Supramolecular Cylindrical Shaped Oligomers and Polymers by Living Ring Opening Metathesis Polymerization of a 7-Oxanorbornene Monomer Substituted with Two Tapered Monodendrons , 1997 .

[53]  E. Chaikof,et al.  Toward an easy access to dendrimer-like poly(ethylene oxide)s. , 2005, Journal of the American Chemical Society.

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

[55]  Yves Gnanou,et al.  Combination of an anionic terminator multifunctional initiator and divergent carbanionic polymerization: application to the synthesis of dendrimer-like polymers and of asymmetric and miktoarm stars. , 2008, Journal of the American Chemical Society.

[56]  V. Percec,et al.  Molecular recognition directed self-assembly of supramolecular cylindrical channel-like architectures from 6,7,9,10,12,13,15,16-octahydro-1,4,7,10,13-pentaoxabenzocyclopentadecen-2-ylmethyl 3,4,5-tris(p-dodecyloxybenzyloxy)benzoate , 1993 .

[57]  V. Percec,et al.  Synthesis of the four‐arm star‐block copolymer [PVC‐b‐PBA‐CH(CH3)COOCH2]4C by SET‐DTLRP initiated from a tetrafunctional initiator , 2009 .

[58]  V. Percec,et al.  Disulfonyl Chlorides: A Universal Class of Initiators for Metal-Catalyzed “Living” Diradical Polymerization of Styrene(s), Methacrylates, and Acrylates , 1997 .

[59]  J. Hedrick,et al.  Dendrimer-like star block and amphiphilic copolymers by combination of ring opening and atom transfer radical polymerization , 1998 .

[60]  V. Percec,et al.  Ultrafast SET-LRP of methyl acrylate at 25 °C in alcohols , 2008 .

[61]  C. Ahn,et al.  Molecular imaging of monodendron jacketed linear polymers by scanning force microscopy , 1998 .

[62]  M. Glodde,et al.  Designing libraries of first generation AB3 and AB2 self-assembling dendrons via the primary structure generated from combinations of (AB)(y)-AB3 and (AB)(y)-AB2 building blocks. , 2004, Journal of the American Chemical Society.

[63]  V. Percec,et al.  Solvent Choice Differentiates SET-LRP and Cu-Mediated Radical Polymerization with Non-First-Order Kinetics , 2008 .

[64]  V. Percec,et al.  Induced helical backbone conformations of self-organizable dendronized polymers. , 2008, Accounts of chemical research.

[65]  J. Hedrick,et al.  Layered Dendritic Block Copolymers. , 1998, Angewandte Chemie.

[66]  V. Percec,et al.  Metal-Catalyzed “Living” Radical Polymerization of Styrene Initiated with Arenesulfonyl Chlorides. From Heterogeneous to Homogeneous Catalysis , 1996 .

[67]  V. Percec,et al.  A comparative computational study of the homolytic and heterolytic bond dissociation energies involved in the activation step of ATRP and SET‐LRP of vinyl monomers , 2007 .

[68]  A. L. Demirel,et al.  Dendrimer-Like Miktoarm Star Terpolymers : A3-(B-C)3via Click Reaction Strategy , 2008 .

[69]  V. Percec,et al.  Functionally terminated poly(methyl acrylate) by SET‐LRP initiated with CHBr3 and CHI3 , 2008 .

[70]  É. Cloutet,et al.  Novel amphiphilic branched copolymers based on polystyrene and poly(ethylene oxide) , 1998 .

[71]  M. R. Imam,et al.  Hollow spherical supramolecular dendrimers. , 2008, Journal of the American Chemical Society.

[72]  V. Percec,et al.  Synthesis of perfectly bifunctional polyacrylates by single-electron-transfer living radical polymerization , 2007 .

[73]  Goran Ungar,et al.  Direct Visualization of Individual Cylindrical and Spherical Supramolecular Dendrimers , 1997 .

[74]  V. Percec,et al.  Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride. , 2002, Journal of the American Chemical Society.

[75]  Yongjun Li,et al.  PNIPAM‐b‐(PEA‐g‐PDMAEA) double‐hydrophilic graft copolymer: Synthesis and its application for preparation of gold nanoparticles in aqueous media , 2009 .

[76]  M. Glodde,et al.  Transformation of a spherical supramolecular dendrimer into a pyramidal columnar supramolecular dendrimer mediated by the fluorophobic effect. , 2003, Angewandte Chemie.

[77]  D. Taton,et al.  Toward an easy access to asymmetric stars and miktoarm stars by atom transfer radical polymerization , 2002 .

[78]  Craig J Hawker,et al.  Efficiency and fidelity in a click-chemistry route to triazole dendrimers by the copper(i)-catalyzed ligation of azides and alkynes. , 2004, Angewandte Chemie.

[79]  V. Percec,et al.  Arenesulfonyl Halides: A Universal Class of Functional Initiators for Metal-Catalyzed “Living” Radical Polymerization of Styrene(s), Methacrylates, and Acrylates† , 1998 .

[80]  V. Percec,et al.  Synthesis and retrostructural analysis of libraries of AB3 and constitutional isomeric AB2 phenylpropyl ether-based supramolecular dendrimers. , 2006, Journal of the American Chemical Society.

[81]  T. Bera,et al.  Universal iterative strategy for the divergent synthesis of dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible TERminator multifunctional INItiator (TERMINI). , 2003, Journal of the American Chemical Society.

[82]  V. Percec,et al.  Design and Structural Analysis of the First Spherical Monodendron Self-Organizable in a Cubic Lattice , 2000 .

[83]  V. Percec,et al.  Thermoreversible cis-cisoidal to cis-transoidal isomerization of helical dendronized polyphenylacetylenes. , 2005, Journal of the American Chemical Society.

[84]  M. R. Imam,et al.  Self-assembly of dendritic crowns into chiral supramolecular spheres. , 2009, Journal of the American Chemical Society.

[85]  G. Mantovani,et al.  Polymerization of methyl acrylate mediated by copper(0)/Me6‐TREN in hydrophobic media enhanced by phenols; Single electron transfer‐living radical polymerization , 2008 .

[86]  V. Percec,et al.  Molecular recognition directed self-assembly of tubular liquid crystalline and crystalline supramolecular architectures from taper shaped (15-crown-5)methyl 3,4,5-tris(p-alkyloxybenzyloxy)benzoates and (15-crown-5)methyl 3,4,5-tris(p-dodecyloxy)benzoate , 1994 .

[87]  V. Percec,et al.  Ultrafast synthesis of ultrahigh molar mass polymers by metal-catalyzed living radical polymerization of acrylates, methacrylates, and vinyl chloride mediated by SET at 25 degrees C. , 2006, Journal of the American Chemical Society.

[88]  G. Ungar,et al.  Rational Design of the First Spherical Supramolecular Dendrimers Self-Organized in a Novel Thermotropic Cubic Liquid-Crystalline Phase and the Determination of Their Shape by X-Ray-Analysis , 1997 .