A Sunlight‐Induced Click Reaction as an Efficient Route to Cyclic Aliphatic Polyesters

To date, the controlled preparation of cyclic polymers is mainly achieved using click ligation strategies. The light-induced Diels-Alder click coupling has recently been shown to function as an attractive catalyst-free alternative to the copper-catalyzed alkyne-azide cycloaddition. However, the need for a light emitting system limits its applicability. To overcome this drawback, a sunlight-induced Diels-Alder reaction as an efficient route for the preparation of cyclic aliphatic polyesters in high yields and purity based on the same chemistry is demonstrated in the present contribution. The versatility and robustness of the proposed strategy against divergent atmospheric conditions is demonstrated. In light of the simplicity of the strategy presented here, it is suggested that the sunlight-induced Diels-Alder click-cyclization is a world-wide transposable process. A sunlight-induced Diels-Alder reaction is demonstrated for the preparation of cyclic polyesters. Under highly divergent atmospheric conditions, cyclic polyesters of high purity are obtained by taking advantage of the natural UV irradiation from the sun. Both summer and winter conditions show impressive performances, allowing to extrapolate the reported protocol to almost any place on earth. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[1]  P. Dubois,et al.  A tandem mass spectrometry-based method to assess the architectural purity of synthetic polymers: a case of a cyclic polylactide obtained by click chemistry , 2015 .

[2]  Kecheng Zhang,et al.  Powerful Ring-Closure Method for Preparing Varied Cyclic Polymers , 2014 .

[3]  L. Mespouille,et al.  One-step synthesis of polylactide macrocycles from sparteine-initiated ROP , 2014 .

[4]  Kim K. Oehlenschlaeger,et al.  Ambient temperature catalyst-free light-induced preparation of macrocyclic aliphatic polyesters. , 2014, Chemical communications.

[5]  Kim K. Oehlenschlaeger,et al.  A mild and efficient approach to functional single-chain polymeric nanoparticles via photoinduced Diels-Alder ligation , 2013 .

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

[7]  Kim K. Oehlenschlaeger,et al.  Light-induced modular ligation of conventional RAFT polymers. , 2013, Angewandte Chemie.

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

[9]  P. Dubois,et al.  Collision-induced dissociation of polymer ions: Charge driven decomposition for sodium-cationized polylactides and isomeric end-group distinction , 2011 .

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

[11]  Kim K. Oehlenschlaeger,et al.  Ambient temperature synthesis of triblock copolymers via orthogonal photochemically and thermally induced modular conjugation , 2011 .

[12]  C. Barner‐Kowollik,et al.  Diels-Alder reactions as an efficient route to high purity cyclic polymers. , 2011, Macromolecular rapid communications.

[13]  C. Hawker,et al.  "Clicking" polymers or just efficient linking: what is the difference? , 2011, Angewandte Chemie.

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

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

[16]  F. Szoka,et al.  The influence of polymer topology on pharmacokinetics: differences between cyclic and linear PEGylated poly(acrylic acid) comb polymers. , 2009, Journal of controlled release : official journal of the Controlled Release Society.

[17]  Scott M. Grayson,et al.  Synthesis and Degradation Behavior of Cyclic Poly(ε-caprolactone) , 2009 .

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

[19]  T. Satoh,et al.  Synthesis of Well-Defined Macrocyclic Poly(δ-valerolactone) by “Click Cyclization” , 2009 .

[20]  F. Szoka,et al.  Dependence of pharmacokinetics and biodistribution on polymer architecture: effect of cyclic versus linear polymers. , 2009, Journal of the American Chemical Society.

[21]  J. Lahann,et al.  Click Chemistry: Versatility and Control in the Hands of Materials Scientists , 2007 .

[22]  T. Brown,et al.  Template-directed oligonucleotide strand ligation, covalent intramolecular DNA circularization and catenation using click chemistry. , 2007, Journal of the American Chemical Society.

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

[24]  M. Finn,et al.  Head-to-tail peptide cyclodimerization by copper-catalyzed azide-alkyne cycloaddition. , 2005, Angewandte Chemie.

[25]  Takahide Mizawa,et al.  Synthesis of α‐maleimide‐ω‐dienyl heterotelechelic poly(methyl methacrylate) and its cyclization by the intramolecular Diels–Alder reaction , 2000 .

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

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