Fast and Selective Organocatalytic Ring-opening Polymerization by Fluorinated Alcohol Without a Cocatalyst

Overview

Journal Nat Commun

Specialty Biology

Date 2019 Aug 11

PMID 31399569

Citations 14

Authors

Wei Zhao

Yanfeng Lv

Ji Li

Zihao Feng

Yonghao Ni

Nikos Hadjichristidis

Affiliations

Soon will be listed here.

Abstract

Organocatalysis is an important branch of catalysis for various organic transformations and materials preparation. Polymerizations promoted by organic catalysts can produce polymeric materials without any metallic residues, providing charming materials for high-value and sensitive domains such as biomedical applications, microelectronic devices and food packaging. Herein, we describe a fluorinated alcohol based catalytic system for polypeptide synthesis via catalytic ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydride (NCA), fulfilling cocatalyst free, metal free, high rate and high selectivity. During polymerization, the fluorinated alcohol catalyst forms multiple dynamic hydrogen bonds with the initiator, monomer and propagating polymer chain. These cooperative hydrogen bonding interactions activate the NCA monomers and simultaneously protect the overactive initiator/propagating polymer chain-ends, which offers the whole polymerization with high activity and selectivity. Mechanistic studies indicate a monocomponent-multifunctional catalytic mode of fluorinated alcohol. This finding provides a metal free and fast approach to access well-defined polypeptides.

Citing Articles

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Kang D, Zhang Y, Yu D, Kim I, Song W J Nanobiotechnology. 2025; 23(1):101.

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Open-vessel polymerization of N-carboxyanhydride (NCA) for polypeptide synthesis.

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A nanoscale MOF-based heterogeneous catalytic system for the polymerization of N-carboxyanhydrides enables direct routes toward both polypeptides and related hybrid materials.

Liu Y, Ren Z, Zhang N, Yang X, Wu Q, Cheng Z Nat Commun. 2023; 14(1):5598.

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References

Schafer A, Wieting J, Fisher T, Mattson A . Chiral silanediols in anion-binding catalysis. Angew Chem Int Ed Engl. 2013; 52(43):11321-4. DOI: 10.1002/anie.201305496. View

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

PAULING L . The Shared-Electron Chemical Bond. Proc Natl Acad Sci U S A. 1928; 14(4):359-62. PMC: 1085493. DOI: 10.1073/pnas.14.4.359. View

Zhang H, Nie Y, Zhi X, Du H, Yang J . Controlled ring-opening polymerization of α-amino acid N-carboxy-anhydride by frustrated amine/borane Lewis pairs. Chem Commun (Camb). 2017; 53(37):5155-5158. DOI: 10.1039/c7cc01440f. View

Giacalone F, Gruttadauria M, Agrigento P, Noto R . Low-loading asymmetric organocatalysis. Chem Soc Rev. 2011; 41(6):2406-47. DOI: 10.1039/c1cs15206h. View

Zou J, Fan J, He X, Zhang S, Wang H, Wooley K . A facile glovebox-free strategy to significantly accelerate the syntheses of well-defined polypeptides by -carboxyanhydride (NCA) ring opening polymerizations. Macromolecules. 2013; 46(10):4223-4226. PMC: 3686519. DOI: 10.1021/ma4007939. View

Phipps R, Hamilton G, Toste F . The progression of chiral anions from concepts to applications in asymmetric catalysis. Nat Chem. 2012; 4(8):603-14. DOI: 10.1038/nchem.1405. View

Berkessel A, Adrio J . Dramatic acceleration of olefin epoxidation in fluorinated alcohols: activation of hydrogen peroxide by multiple h-bond networks. J Am Chem Soc. 2006; 128(41):13412-20. DOI: 10.1021/ja0620181. View

Othon C, Kwon O, Lin M, Zewail A . Solvation in protein (un)folding of melittin tetramer-monomer transition. Proc Natl Acad Sci U S A. 2009; 106(31):12593-8. PMC: 2722364. DOI: 10.1073/pnas.0905967106. View

10.

Lu H, Cheng J . Hexamethyldisilazane-mediated controlled polymerization of alpha-amino acid N-carboxyanhydrides. J Am Chem Soc. 2007; 129(46):14114-5. DOI: 10.1021/ja074961q. View

11.

Deming T . Facile synthesis of block copolypeptides of defined architecture. Nature. 1997; 390(6658):386-9. DOI: 10.1038/37084. View

12.

Dong S, Feng X, Liu X . Chiral guanidines and their derivatives in asymmetric synthesis. Chem Soc Rev. 2018; 47(23):8525-8540. DOI: 10.1039/c7cs00792b. View

13.

Lu H, Wang J, Song Z, Yin L, Zhang Y, Tang H . Recent advances in amino acid N-carboxyanhydrides and synthetic polypeptides: chemistry, self-assembly and biological applications. Chem Commun (Camb). 2013; 50(2):139-55. DOI: 10.1039/c3cc46317f. View

14.

Wurm F, Klok H . Be squared: expanding the horizon of squaric acid-mediated conjugations. Chem Soc Rev. 2013; 42(21):8220-36. DOI: 10.1039/c3cs60153f. View

15.

Hillmyer M, Tolman W . Aliphatic polyester block polymers: renewable, degradable, and sustainable. Acc Chem Res. 2014; 47(8):2390-6. DOI: 10.1021/ar500121d. View

16.

Matyjaszewski K, Tsarevsky N . Macromolecular engineering by atom transfer radical polymerization. J Am Chem Soc. 2014; 136(18):6513-33. DOI: 10.1021/ja408069v. View

17.

Connon S . Organocatalysis mediated by (thio)urea derivatives. Chemistry. 2006; 12(21):5418-27. DOI: 10.1002/chem.200501076. View

18.

Satoh K, Kamigaito M . Stereospecific living radical polymerization: dual control of chain length and tacticity for precision polymer synthesis. Chem Rev. 2009; 109(11):5120-56. DOI: 10.1021/cr900115u. View

19.

Yoon T, Jacobsen E . Privileged chiral catalysts. Science. 2003; 299(5613):1691-3. DOI: 10.1126/science.1083622. View

20.

Kricheldorf H . Polypeptides and 100 years of chemistry of alpha-amino acid N-carboxyanhydrides. Angew Chem Int Ed Engl. 2006; 45(35):5752-84. DOI: 10.1002/anie.200600693. View