Fast and selective organocatalytic ring-opening polymerization by fluorinated alcohol without a cocatalyst.

Wei Zhao; Yanfeng Lv; Ji Li; Zihao Feng; Yonghao Ni; Nikos Hadjichristidis

doi:10.1038/s41467-019-11524-y

Fast and selective organocatalytic ring-opening polymerization by fluorinated alcohol without a cocatalyst.

Wei Zhao, Yanfeng Lv, Ji Li, Zihao Feng, Yonghao Ni, Nikos Hadjichristidis

Research output: Contribution to journal › Article › peer-review

77 Scopus citations

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.

Original language	English (US)
Journal	Nature communications
Volume	10
Issue number	1
DOIs	https://doi.org/10.1038/s41467-019-11524-y
State	Published - Aug 9 2019

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work is supported by grants from the National Natural Science Foundation of China (No. 21774071) and Natural Science Foundation of Shaanxi University of Science and Technology (No. 2017QNBJ-07). W.Z. thanks the support from the Youth HundredTalent Program of Shaanxi Province (No.SXBR9227), the National High-Level Foreign Expert Project (No.GDT20186100425), Biomass Chemistry and Materials Academician Workstation Project in SUST (No.134090002) and Northwest Polytechnic University High Performance Computing and Development Center. N.H. acknowledges the support of King Abdullah University of Science and Technology.

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Cite this

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title = "Fast and selective organocatalytic ring-opening polymerization by fluorinated alcohol without a cocatalyst.",

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.",

author = "Wei Zhao and Yanfeng Lv and Ji Li and Zihao Feng and Yonghao Ni and Nikos Hadjichristidis",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: This work is supported by grants from the National Natural Science Foundation of China (No. 21774071) and Natural Science Foundation of Shaanxi University of Science and Technology (No. 2017QNBJ-07). W.Z. thanks the support from the Youth HundredTalent Program of Shaanxi Province (No.SXBR9227), the National High-Level Foreign Expert Project (No.GDT20186100425), Biomass Chemistry and Materials Academician Workstation Project in SUST (No.134090002) and Northwest Polytechnic University High Performance Computing and Development Center. N.H. acknowledges the support of King Abdullah University of Science and Technology.",

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AU - Ni, Yonghao

AU - Hadjichristidis, Nikos

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: This work is supported by grants from the National Natural Science Foundation of China (No. 21774071) and Natural Science Foundation of Shaanxi University of Science and Technology (No. 2017QNBJ-07). W.Z. thanks the support from the Youth HundredTalent Program of Shaanxi Province (No.SXBR9227), the National High-Level Foreign Expert Project (No.GDT20186100425), Biomass Chemistry and Materials Academician Workstation Project in SUST (No.134090002) and Northwest Polytechnic University High Performance Computing and Development Center. N.H. acknowledges the support of King Abdullah University of Science and Technology.

PY - 2019/8/9

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N2 - 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.

AB - 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.

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Fast and selective organocatalytic ring-opening polymerization by fluorinated alcohol without a cocatalyst.

Abstract

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