Bifunctional Fluoroalcohol Catalysts Enabled Sustainable Synthesis of Poly(amino acid)s†

Main observation and conclusion A series of novel bifunctional single-molecule hydrogen-bonding organocatalysts based on fluorinated tertiary alcohol were synthesized to mediate the metal-free polymerization of alpha-amino acid N-carboxyanhydride (NCA) monomer. Through the screening of catalysts, the polymerization catalyzed by the preferred bifunctional fluoroalcohol catalyst proceeded in a fast and controlled manner, affording high molecular weight polypeptide up to 35.2 x 10(4) Da with relatively narrow molecular weight distribution (D < 1.20). A phenomenon of self-accelerating effect of polymerization induced by alpha-helical structure of polypeptides was observed, and a possible polymerization pathway has been discussed.

Automated summary

A series of novel bifunctional single-molecule hydrogen-bonding organocatalysts based on fluorinated tertiary alcohol were synthesized for the metal-free polymerization of alpha-amino acid N-carboxyanhydride (NCA) monomer. The preferred bifunctional fluoroalcohol catalyst mediated polymerization in a fast and controlled manner, resulting in high molecular weight polypeptides with relatively narrow molecular weight distribution. A self-accelerating effect of polymerization induced by the alpha-helical structure of polypeptides was observed, and a possible polymerization pathway was discussed.