Precise synthesis of molecularly defined oligomers and polymers by orthogonal iterative divergent/convergent approaches.

The synthesis of perfectly defined (macro)molecules has been a constant challenge for polymer and organic chemists. This paper highlights the main applications of the iterative divergent/convergent approach for the synthesis of discrete mass oligomers and polymers. We will discuss the orthogonal deprotection and coupling strategies involved in this powerful strategy where chain length doubles at each iteration and which has been applied to the synthesis of conjugated rigid rods as well as amorphous and crystalline oligomers and polymers. The synthesis of perfectly defined oligomers in respect to emerging highly efficient and orthogonal chemistries will also be highlighted.

[1]  W. Fix,et al.  Fast polymer integrated circuits , 2002 .

[2]  Timothy E. Long,et al.  Modern polyesters : chemistry and technology of polyesters and copolyesters , 2004 .

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

[4]  Jean M. J. Fréchet,et al.  A “Branched-Monomer Approach” for the Rapid Synthesis of Dendimers† , 1994 .

[5]  Uglea Oligomer Technology and Applications , 1998 .

[6]  H. Sirringhaus,et al.  Self-Aligned, Vertical-Channel, Polymer Field-Effect Transistors , 2003, Science.

[7]  Jia-cong Shen,et al.  Rapid synthesis of polyester dendrimers , 1997 .

[8]  C. Slugovc The Ring Opening Metathesis Polymerisation Toolbox , 2004 .

[9]  C. Pan,et al.  Tadpole‐shaped amphiphilic copolymers prepared via RAFT polymerization and click reaction , 2008 .

[10]  Graeme Moad,et al.  Living radical polymerization by the RAFT process , 2005 .

[11]  Odile Dechy-Cabaret,et al.  Controlled ring-opening polymerization of lactide and glycolide. , 2004, Chemical reviews.

[12]  A. Schlüter,et al.  Shape‐Persistent, Nano‐Sized Macrocycles , 2002 .

[13]  R. Grubbs,et al.  Living ring-opening metathesis polymerization , 2007 .

[14]  D. Seebach,et al.  Detection, synthesis, structure, and function of oligo(3-hydroxyalkanoates): contributions by synthetic organic chemists. , 1999, International journal of biological macromolecules.

[15]  Craig J Hawker,et al.  A modular approach to functionalized and expanded crown ether based macrocycles using click chemistry. , 2009, Angewandte Chemie.

[16]  R. B. Merrifield Solid Phase Synthesis (Nobel Lecture) , 1985 .

[17]  M. Whiting,et al.  Syntheses of very long chain alkanes terminating in polydeuterium-labelled end-groups and some very large single-branched alkanes including Y-shaped structures , 2001 .

[18]  P. Arora,et al.  Solution- and solid-phase synthesis of triazole oligomers that display protein-like functionality. , 2007, The Journal of organic chemistry.

[19]  C. Pan,et al.  Synthesis of Well‐Defined Figure‐of‐Eight‐Shaped Polymers by a Combination of ATRP and Click Chemistry , 2008 .

[20]  A. Flood,et al.  Click chemistry generates privileged CH hydrogen-bonding triazoles: the latest addition to anion supramolecular chemistry. , 2010, Chemical Society reviews.

[21]  Craig J. Hawker,et al.  Molecularly defined (L)‐lactic acid oligomers and polymers: Synthesis and characterization , 2008 .

[22]  Beck,et al.  Convenient iterative synthesis of an octameric tetracarboxylate-functionalized oligophenylene rod with divergent end groups , 2000, Organic letters.

[23]  Igor F. Perepichka,et al.  Handbook of Thiophene-Based Materials , 2009 .

[24]  H. Klok,et al.  A Post‐Modification Strategy for the Synthesis of Uniform, Hydrophilic/Hydrophobic Patterned α‐Hydroxy Acid Oligomers , 2009 .

[25]  G. Ungar,et al.  Learning polymer crystallization with the aid of linear, branched and cyclic model compounds. , 2001, Chemical reviews.

[26]  Jeffrey S. Moore,et al.  A water-soluble m-phenylene ethynylene foldamer. , 2004, Organic letters.

[27]  Jason E Hein,et al.  Iterative in situ click chemistry creates antibody-like protein-capture agents. , 2009, Angewandte Chemie.

[28]  E. W. Meijer,et al.  About Oligothiophene Self-Assembly: From Aggregation in Solution to Solid-State Nanostructures , 2004 .

[29]  Fosong Wang,et al.  Synthesis of Monodisperse Oligo[(1,4‐Phenyleneethynylene)‐Alt‐(2,5‐Thiopheneethynylene)]s , 2005 .

[30]  D. Holdup,et al.  Studies on the synthesis of linear aliphatic compounds. Part. 3 The synthesis of paraffins with very long chains , 1987 .

[31]  Studies on the synthesis of linear aliphatic compounds. Part 2. The realisation of a strategy for repeated molecular doubling. , 1987 .

[32]  M. Whiting,et al.  Synthesis of oligomers related to nylon 6 , 1997 .

[33]  A. MacDiarmid,et al.  Oligomers and isomers: new horizons in poly-anilines , 1999 .

[34]  E. J. Chung,et al.  Advances and Applications of Biodegradable Elastomers in Regenerative Medicine , 2010 .

[35]  Igor F. Perepichka,et al.  Handbook of thiophene-based materials : applications in organic electronics and photonics , 2009 .

[36]  G. Schopf,et al.  Polythiophenes ― Electrically Conductive Polymers , 1996 .

[37]  C. F. van der Walle,et al.  Engineering biodegradable polyester particles with specific drug targeting and drug release properties. , 2008, Journal of pharmaceutical sciences.

[38]  W. Binder,et al.  'Click' Chemistry in Polymer and Material Science: An Update , 2008 .

[39]  A. Müller,et al.  Anionic vinyl polymerization—50 years after Michael Szwarc , 2007 .

[40]  J. Hedrick,et al.  Synthesis of well-defined hydrogel networks using click chemistry. , 2006, Chemical communications.

[41]  Jean-François Lutz,et al.  Sequence control in polymer synthesis. , 2009, Chemical Society reviews.

[42]  D. Seebach,et al.  Preparation of Free and of Specifically Protected Oligo[β‐Malic Acids] for Enzymatic Degradation Studies , 2000 .

[43]  Patrice Rannou,et al.  Processible conjugated polymers: from organic semiconductors to organic metals and superconductors , 2002 .

[44]  C. Weder,et al.  Poly(arylene ethynylene)s : from synthesis to application , 2005 .

[45]  C. Weder Poly(arylene etynylene)s , 2005 .

[46]  Synthesis and chiroptical properties of optically active, regioregular oligothiophenes. , 2001, Organic letters.

[47]  J. Fréchet,et al.  Two-step approach towards the accelerated synthesis of dendritic macromolecules , 1993 .

[48]  A. Kirschning,et al.  Sustainable concepts in olefin metathesis. , 2007, Angewandte Chemie.

[49]  Dennis J. Gravert,et al.  Organic Synthesis on Soluble Polymer Supports: Liquid-Phase Methodologies. , 1997, Chemical reviews.

[50]  Kenichi Takizawa,et al.  Molecularly defined caprolactone oligomers and polymers: synthesis and characterization. , 2008, Journal of the American Chemical Society.

[51]  David M. Hercules,et al.  Synthesis and secondary-ion mass spectrometry of linear single oligomers of nylon-6 , 1999 .

[52]  G. Siuzdak,et al.  Asymmetric Dihydroxylation Enables Rapid Construction of Chiral Dendrimers Based on 1,2‐Diols , 1996 .

[53]  Hans-Joachim Egelhaaf,et al.  Optical Bandgaps of π‐Conjugated Organic Materials at the Polymer Limit: Experiment and Theory , 2007 .

[54]  C. Barner‐Kowollik,et al.  Access to cyclic polystyrenes via a combination of reversible addition fragmentation chain transfer (RAFT) polymerization and click chemistry , 2008 .

[55]  Yuting Liang,et al.  Conformational and supramolecular properties of main chain and cyclic click oligotriazoles and polytriazoles. , 2010, Chemical communications.

[56]  Jeffrey S. Moore,et al.  Geometrically-Controlled and Site-Specifically-Functionalized Phenylacetylene Macrocycles , 1994 .

[57]  A. L. Demirel,et al.  Poly(2-oxazoline)s as Smart Bioinspired Polymers. , 2010, Macromolecular rapid communications.

[58]  Craig J. Hawker,et al.  EXACT LINEAR ANALOGS OF DENDRITIC POLYETHER MACROMOLECULES : DESIGN, SYNTHESIS, AND UNIQUE PROPERTIES , 1997 .

[59]  E. Harth,et al.  New polymer synthesis by nitroxide mediated living radical polymerizations. , 2001, Chemical reviews.

[60]  P. Franke,et al.  REPETITIVE STRATEGY FOR EXPONENTIAL GROWTH OF HYDROXY-FUNCTIONALIZED DENDRONS , 1996 .

[61]  J. Fréchet,et al.  Convergent dendrons and dendrimers: from synthesis to applications. , 2001, Chemical reviews.

[62]  Arthur J. Epstein,et al.  'Synthetic metals': a novel role for organic polymers , 1989 .

[63]  M. Mutter,et al.  Liquid Phase Synthesis of Peptides , 1972, Nature.

[64]  F. Diederich,et al.  Modern Supramolecular Chemistry: Strategies for Macrocycle Synthesis , 2008 .

[65]  M. Kakimoto,et al.  Rapid synthesis of Aromatic polyamide dendrimers by an orthogonal and a double-stage convergent approach , 2000 .

[66]  B. Wunderlich,et al.  Melting and Crystallization of Polyethylene of Different Molar Mass by Calorimetry , 2001 .

[67]  V. Percec,et al.  Monodisperse Linear Liquid Crystalline Polyethers via a Repetitive 2n Geometric Growth Algorithm , 1997 .

[68]  Steven C. Zimmerman,et al.  Rapid synthesis of dendrimers by an orthogonal coupling strategy , 1996 .

[69]  C. Hawker,et al.  Design of crosslinked hybrid multilayer thin films from azido-functionalized polystyrenes and platinum nanoparticles , 2009 .

[70]  Casey K. Chan,et al.  Degradation behaviors of electrospun resorbable polyester nanofibers. , 2009, Tissue engineering. Part B, Reviews.

[71]  J. Tour,et al.  Molecular electronics. Synthesis and testing of components. , 2000, Accounts of chemical research.

[72]  Morten Meldal,et al.  Peptidotriazoles on solid phase: [1,2,3]-triazoles by regiospecific copper(i)-catalyzed 1,3-dipolar cycloadditions of terminal alkynes to azides. , 2002, The Journal of organic chemistry.

[73]  Mark A. Ratner,et al.  Molecular-wire behaviour in p -phenylenevinylene oligomers , 1998, Nature.

[74]  Krzysztof Matyjaszewski,et al.  Nanostructured functional materials prepared by atom transfer radical polymerization , 2009, Nature Chemistry.

[75]  J. Mays,et al.  Macromolecular Architectures by Living and Controlled/Living Polymerizations , 2006 .

[76]  J. Tour,et al.  Iterative Divergent/Convergent Approach to Linear Conjugated Oligomers by Successive Doubling of the Molecular Length: A Rapid Route to a 128Å‐Long Potential Molecular Wire , 1994 .

[77]  K. Burgess,et al.  An iterative route to "decorated" ethylene glycol-based linkers. , 2006, Chemical communications.

[78]  Heinz-Georg Nothofer,et al.  Improving the performance of doped π-conjugated polymers for use in organic light-emitting diodes , 2000, Nature.

[79]  D. Seebach,et al.  Synthese monodisperser linearer und cyclischer Oligomere der (R)‐3‐Hydroxybuttersäure mit bis zu 128 Einheiten , 1996 .

[80]  Charles L. Wilkins,et al.  Double Exponential Dendrimer Growth , 1995 .

[81]  S. Buchwald,et al.  Palladium-Catalyzed Synthesis of Monodisperse, Controlled-Length, and Functionalized Oligoanilines , 1998 .

[82]  S. Aoshima,et al.  A renaissance in living cationic polymerization. , 2009, Chemical reviews.

[83]  P. Dubois,et al.  Handbook of ring-opening polymerization , 2009 .

[84]  U. Schubert,et al.  Poly(2-oxazolines) in biological and biomedical application contexts. , 2007, Advanced drug delivery reviews.

[85]  Y. Grohens,et al.  Influence of progressive cross-linking on dewetting of polystyrene thin films. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[86]  Chang-Qi Ma,et al.  Functional oligothiophenes: molecular design for multidimensional nanoarchitectures and their applications. , 2009, Chemical reviews.

[87]  R. Roy,et al.  Novel Dendritic alpha-Sialosides: Synthesis of Glycodendrimers Based on a 3,3'-Iminobis(propylamine) Core. , 1996, The Journal of organic chemistry.

[88]  Jeffrey S. Moore,et al.  Shape-persistent macrocycles: structures and synthetic approaches from arylene and ethynylene building blocks. , 2006, Angewandte Chemie.

[89]  Daoyong Chen,et al.  High-efficiency preparation of macrocyclic diblock copolymers via selective click reaction in micellar media. , 2009, Journal of the American Chemical Society.

[90]  F. Cui,et al.  Surface modification of polyester biomaterials for tissue engineering , 2007, Biomedical materials.

[91]  R. B. Merrifield Solid phase peptide synthesis. I. the synthesis of a tetrapeptide , 1963 .

[92]  J. Pascault,et al.  Kinetic study of copper(I)‐catalyzed click chemistry step‐growth polymerization , 2008 .

[93]  A. Peacock Handbook of Polyethylene: Structures: Properties, and Applications , 2000 .

[94]  O. I. Paynter,et al.  The synthesis of long-chain unbranched aliphatic compounds by molecular doubling , 1982 .

[95]  U. Bunz,et al.  Poly(aryleneethynylene)s: Syntheses, Properties, Structures, and Applications. , 2000, Chemical reviews.

[96]  Luke G Green,et al.  A stepwise huisgen cycloaddition process: copper(I)-catalyzed regioselective "ligation" of azides and terminal alkynes. , 2002, Angewandte Chemie.

[97]  Jeffrey S. Moore,et al.  Efficient synthesis of nanoscale macrocyclic hydrocarbons , 1992 .

[98]  M. Charreyre,et al.  Experimental Requirements for an Efficient Control of Free‐Radical Polymerizations via the Reversible Addition‐Fragmentation Chain Transfer (RAFT) Process , 2006 .

[99]  A. Hult,et al.  Double-Stage Convergent Approach for the Synthesis of Functionalized Dendritic Aliphatic Polyesters Based on 2,2-Bis(hydroxymethyl)propionic Acid , 1998 .

[100]  Y. Aso,et al.  Functional oligothiophenes as advanced molecular electronic materials , 2002 .

[101]  E. W. Meijer,et al.  About Supramolecular Assemblies of π-Conjugated Systems , 2005 .

[102]  K. Kimura,et al.  Morphology Control of Aromatic Polymers in Concert with Polymerization , 2006 .

[103]  J. Tour,et al.  Rapid Syntheses of Oligo(2,5-thiophene ethynylene)s with Thioester Termini: Potential Molecular Scale Wires with Alligator Clips , 1997 .

[104]  Rainer E. Martin,et al.  Linear Monodisperse π-Conjugated Oligomers: Model Compounds for Polymers and More. , 1999, Angewandte Chemie.

[105]  J. Tour,et al.  Iterative Divergent/Convergent Approach to Conjugated Oligomers by a Doubling of Molecular Length at Each Iteration. A Rapid Route to Potential Molecular Wires , 1994 .

[106]  Bin Huang,et al.  Homogeneous polyesters of predetermined length, composition, and sequence : model synthesis of alternating glycolic-acid-co-(L)-lactic-acid oligomers , 1995 .

[107]  J. Tour,et al.  Rapid Solution and Solid Phase Syntheses of Oligo(1,4-phenylene ethynylene)s with Thioester Termini: Molecular Scale Wires with Alligator Clips. Derivation of Iterative Reaction Efficiencies on a Polymer Support , 1997 .

[108]  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 .

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

[110]  B. S. Balaji,et al.  Double exponential growth of aliphatic polyamide dendrimers via AB(2) hypermonomer strategy. , 2009, Chemical communications.

[111]  J. Hartwig,et al.  The Largest Discrete Oligo(m-aniline). An Exponential Growth Strategy Using Palladium-Catalyzed Amination of Aryl Sulfonates , 1998 .

[112]  F. Tanaka,et al.  Temperature-Induced Phase Transition of Well-Defined Cyclic Poly(N-isopropylacrylamide)s in Aqueous Solution , 2007 .

[113]  Denis Fichou,et al.  Handbook of oligo- and polythiophenes , 1998 .

[114]  M. Stanford,et al.  Synthesis of stereoregular cyclic poly(lactide)s via "thiol-ene" click chemistry , 2010 .

[115]  David M. Hercules,et al.  Synthesis of Discrete Mass Poly(butylene glutarate) Oligomers , 2003 .

[116]  M. Whiting,et al.  A versatile process for the syntheses of very long chain alkanes, functionalised derivatives and some branched chain hydrocarbons , 1996 .

[117]  A. Godt,et al.  Synthesis and Characterization of Monodisperse Oligo(phenyleneethynylene)s , 1997 .

[118]  Mark C. Whiting,et al.  The synthesis of pure n-paraffins with chain-lengths between one and four hundred , 1985 .

[119]  Jun Sakamoto,et al.  Suzuki Polycondensation: Polyarylenes à la Carte. , 2009, Macromolecular rapid communications.

[120]  Chen Li,et al.  Polyphenylene-based materials for organic photovoltaics. , 2010, Chemical reviews.

[121]  A. MacDiarmid,et al.  Sensors using octaaniline for volatile organic compounds , 1999 .

[122]  Jian Yang,et al.  Biodegradable polyester elastomers in tissue engineering , 2004, Expert opinion on biological therapy.

[123]  Fosong Wang,et al.  A novel in situ deprotection/coupling and iterative divergent/convergent strategy for the synthesis of oligo(1,4-phenyleneethynylene)s , 2005 .

[124]  Daniel J. Burke,et al.  Applications of orthogonal "click" chemistries in the synthesis of functional soft materials. , 2009, Chemical reviews.

[125]  Jeffrey S. Moore,et al.  Nanoarchitectures. 1. Controlled synthesis of phenylacetylene sequences , 1992 .

[126]  Wolfgang Clemens,et al.  Stability of polythiophene-based transistors and circuits , 2003 .

[127]  E. W. Meijer,et al.  Supramolecular electronics; nanowires from self-assembled pi-conjugated systems. , 2005, Chemical communications.

[128]  Jeffrey S. Moore,et al.  Shape-persistent arylene ethynylene macrocycles: syntheses and supramolecular chemistry. , 2003, Chemical communications.

[129]  A. Vasella,et al.  Oligosaccharide Analogues of Polysaccharides. Part 6. Orthogonal protecting/activating groups in an improved binomial synthesis of ‘acetyleno‐oligosaccharides’ , 1996 .

[130]  J. Tour Conjugated Macromolecules of Precise Length and Constitution. Organic Synthesis for the Construction of Nanoarchitectures. , 1996, Chemical reviews.

[131]  B. Amsden,et al.  Biodegradable elastomers in drug delivery , 2008, Expert opinion on drug delivery.

[132]  Jing Ye,et al.  Synthesis of Well-Defined Cyclic Poly(N-isopropylacrylamide) via Click Chemistry and Its Unique Thermal Phase Transition Behavior , 2007 .

[133]  F. Dörwald Organic Synthesis on Solid Phase , 2002 .

[134]  S. Hecht,et al.  Exponential growth of functional poly(glutamic acid)dendrimers with variable stereochemistry , 2010 .

[135]  Zhixiang Wei,et al.  Aniline Oligomers – Architecture, Function and New Opportunities for Nanostructured Materials , 2008 .

[136]  E. W. Meijer,et al.  Two-dimensional charge transport in self-organized, high-mobility conjugated polymers , 1999, Nature.

[137]  Christopher L. Brown,et al.  The Synthesis and Characterization of a New Family of Polyamide Dendrimers , 1998 .

[138]  G. Lessene,et al.  Synthesis of azide-alkyne fragments for ‘click’ chemical applications; formation of oligomers from orthogonally protected trialkylsilyl-propargyl azides and propargyl alcohols , 2006 .

[139]  B. Sumerlin,et al.  Macromolecular Engineering through Click Chemistry and Other Efficient Transformations , 2010 .

[140]  K. Bechgaard,et al.  Condensed-matter physics: Superconducting plastic , 2001, Nature.

[141]  Jean-François Lutz,et al.  Liquid-phase synthesis of block copolymers containing sequence-ordered segments. , 2009, Journal of the American Chemical Society.