The development of the following two novel initiating/organocatalytic systems for the fast and living ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCAs) at room temperature will be discussed: a). Primary and tertiary amines in the same molecule. By associating primary (slow but controlled ROP) and tertiary (fast but uncontrolled ROP) amines in the same molecule, novel highly active organocatalytic system proceeding by an accelerated amine mechanism through monomer activation (AAMMA) and leading to well-defined polypeptides at room temperature were developed. b). Aminoalcohols in the presence of N,N’-bis[3,5-bis(trifluoromethyl)phenyl]thiourea. The thiourea provides, through hydrogen bonding, simultaneous activation of NCA monomers/reversible deactivation of polymer chain ends/silencing of the secondary/tertiary amine and thus allows the polymerization to proceed in a highly controllable manner. This method provides an efficient way to synthesize novel alkyne-functionalized homopolypeptides (A) and copolypeptides, such as AB diblock (B: non-functionalized), ABA triblock and star-AB diblock, as well as linear and star random copolypeptides, which are precursors of a plethora of complex macromolecular architectures by click chemistry.

Novel initiating/organocatalytic systems for the living ring-opening polymerization of α−amino acid N−carboxyanhydrides

254th National Meeting (2017)

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