Isoselective Lactide Ring Opening Polymerisation Using [2]Rotaxane Catalysts

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2019 Mar 13

PMID 30861303

Citations 20

Authors

Jason Y C Lim

Nattawut Yuntawattana

Paul D Beer

Charlotte K Williams

Affiliations

Soon will be listed here.

Abstract

Polylactide (PLA) is a fully biodegradable and recyclable plastic, produced from a bio-derived monomer: it is a circular economy plastic. Its properties depend upon its stereochemistry and isotactic PLA shows superior thermal-mechanical performances. Here, a new means to control tacticity by exploiting rotaxane conformational dynamism is described. Dynamic achiral [2]rotaxanes can show high isoselectivity (P =0.8, 298 K) without requiring any chiral additives and enchain by a chain end control mechanism. The organocatalytic dynamic stereoselectivity is likely applicable to other small-molecule and polymerization catalyses.

Citing Articles

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Kinetically controlled synthesis of rotaxane geometric isomers.

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References

Zhu J, Chen E . From meso-Lactide to Isotactic Polylactide: Epimerization by B/N Lewis Pairs and Kinetic Resolution by Organic Catalysts. J Am Chem Soc. 2015; 137(39):12506-9. DOI: 10.1021/jacs.5b08658. View

De Bo G, Gall M, Kitching M, Kuschel S, Leigh D, Tetlow D . Sequence-Specific β-Peptide Synthesis by a Rotaxane-Based Molecular Machine. J Am Chem Soc. 2017; 139(31):10875-10879. DOI: 10.1021/jacs.7b05850. View

Stanford M, Dove A . Stereocontrolled ring-opening polymerisation of lactide. Chem Soc Rev. 2010; 39(2):486-94. DOI: 10.1039/b815104k. View

Castro-Aguirre E, Iniguez-Franco F, Samsudin H, Fang X, Auras R . Poly(lactic acid)-Mass production, processing, industrial applications, and end of life. Adv Drug Deliv Rev. 2016; 107:333-366. DOI: 10.1016/j.addr.2016.03.010. View

Kan Z, Luo W, Shi T, Wei C, Han B, Zheng D . Facile Preparation of Stereoblock PLA From Ring-Opening Polymerization of -Lactide by a Synergetic Binary Catalytic System Containing Ureas and Alkoxides. Front Chem. 2018; 6:547. PMC: 6240762. DOI: 10.3389/fchem.2018.00547. View

Myers D, White A, Forsyth C, Bown M, Williams C . Phosphasalen Indium Complexes Showing High Rates and Isoselectivities in rac-Lactide Polymerizations. Angew Chem Int Ed Engl. 2017; 56(19):5277-5282. PMC: 5434947. DOI: 10.1002/anie.201701745. View

Bakewell C, Cao T, Long N, Le Goff X, Auffrant A, Williams C . Yttrium phosphasalen initiators for rac-lactide polymerization: excellent rates and high iso-selectivities. J Am Chem Soc. 2012; 134(51):20577-80. DOI: 10.1021/ja310003v. View

Ramakrishnam Raju M, Lin H . A novel diketopyrrolopyrrole (DPP)-based [2]rotaxane for highly selective optical sensing of fluoride. Org Lett. 2013; 15(6):1274-7. DOI: 10.1021/ol400221h. View

Kassem S, Van Leeuwen T, Lubbe A, Wilson M, Feringa B, Leigh D . Artificial molecular motors. Chem Soc Rev. 2017; 46(9):2592-2621. DOI: 10.1039/c7cs00245a. View

10.

Chen N, Huang P, Lai C, Liu Y, Wang Y, Peng S . A [2]rotaxane-based (1)H NMR spectroscopic probe for the simultaneous identification of physiologically important metal ions in solution. Chem Commun (Camb). 2007; (40):4122-4. DOI: 10.1039/b706461f. View

11.

Kay E, Leigh D . Rise of the Molecular Machines. Angew Chem Int Ed Engl. 2015; 54(35):10080-8. PMC: 4557038. DOI: 10.1002/anie.201503375. View

12.

Zhang L, Nederberg F, Messman J, Pratt R, Hedrick J, Wade C . Organocatalytic stereoselective ring-opening polymerization of lactide with dimeric phosphazene bases. J Am Chem Soc. 2007; 129(42):12610-1. DOI: 10.1021/ja074131c. View

13.

Ma H, Spaniol T, Okuda J . Highly heteroselective ring-opening polymerization of rac-lactide initiated by bis(phenolato)scandium complexes. Angew Chem Int Ed Engl. 2006; 45(46):7818-21. DOI: 10.1002/anie.200603178. View

14.

Dove A, Li H, Pratt R, Lohmeijer B, Culkin D, Waymouth R . Stereoselective polymerization of rac- and meso-lactide catalyzed by sterically encumbered N-heterocyclic carbenes. Chem Commun (Camb). 2006; (27):2881-3. DOI: 10.1039/b601393g. View

15.

Spink S, Kazakov O, Kiesewetter E, Kiesewetter M . Rate Accelerated Organocatalytic Ring-Opening Polymerization of L-Lactide via the Application of a Bis(thiourea) H-bond Donating Cocatalyst. Macromolecules. 2016; 48(17):6127-6131. PMC: 4863465. DOI: 10.1021/acs.macromol.5b01320. View

16.

Sanchez-Sanchez A, Rivilla I, Agirre M, Basterretxea A, Etxeberria A, Veloso A . Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Amino Acids. J Am Chem Soc. 2017; 139(13):4805-4814. DOI: 10.1021/jacs.6b13080. View

17.

Zhang X, Jones G, Hedrick J, Waymouth R . Fast and selective ring-opening polymerizations by alkoxides and thioureas. Nat Chem. 2016; 8(11):1047-1053. DOI: 10.1038/nchem.2574. View

18.

Sarazin Y, Carpentier J . Discrete cationic complexes for ring-opening polymerization catalysis of cyclic esters and epoxides. Chem Rev. 2015; 115(9):3564-614. DOI: 10.1021/acs.chemrev.5b00033. View

19.

Erbas-Cakmak S, Leigh D, McTernan C, Nussbaumer A . Artificial Molecular Machines. Chem Rev. 2015; 115(18):10081-206. PMC: 4585175. DOI: 10.1021/acs.chemrev.5b00146. View

20.

Barendt T, Docker A, Marques I, Felix V, Beer P . Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle. Angew Chem Int Ed Engl. 2016; 55(37):11069-76. PMC: 5113793. DOI: 10.1002/anie.201604327. View