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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 ?-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.

SUBMITTER: Zhao W

PROVIDER: S-EPMC6689068 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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

Zhao Wei W Lv Yanfeng Y Li Ji J Feng Zihao Z Ni Yonghao Y Hadjichristidis Nikos N

Nature communications 20190809 1

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 ...[more]

PMID: 31399569

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Project description:Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes, such as hexamethylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, and 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, using water as an initiator and strong organic bases, such as amidines, guanidines, phosphazene bases, and proazaphosphatrane, as catalysts produced a variety of polysiloxanes with controlled number-average molecular weights (Mn = 2.64-102.3 kg mol-1), narrow polydispersity (? = 1.03-1.16), and well-defined symmetric structures. Controlled syntheses of statistical copolymers and triblock copolymers were achieved by copolymerizations of two cyclotrisiloxanes. Various terminal functionalities were successfully introduced by the end-capping reaction of propagating polysiloxanes using functional chlorosilanes. Kinetic investigations demonstrated that the polymerization proceeded through the initiator/chain-end activation mechanism, namely activations of water in the initiation reaction and of terminal silanols in propagating polysiloxanes in the propagation reaction. Catalytic activities of strong organic bases were revealed to depend on their Brønsted basicity and efficiency of the proton transfer in the initiation and propagation reactions. Guanidines possessing an R-N 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C(N)-NH-R' unit, in particular 1,3-trimethylene-2-propylguanidine, showed excellent performance as a catalyst. In this system, even non-dehydrated solvents are usable for the polymerization.

Dataset Information

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

Publications

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

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