N-Trimethylsilyl Amines for Controlled Ring-Opening Polymerization of Amino Acid N-Carboxyanhydrides and Facile End Group Functionalization of Polypeptides

• Published in: Journal of the American Chemical Society Vol. 130; no. 38; pp. 12562 - 12563
• Main Authors: Lu, Hua, Cheng, Jianjun
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 24-09-2008
• Subjects: Allylamine - chemistry; Amines - chemistry; Amino Acids - chemistry; Anhydrides - chemistry; Carbamates - chemistry; Cyclization; Glutamates - chemistry; Peptides - chemical synthesis; Peptides - chemistry; Polyglutamic Acid - analogs & derivatives; Polyglutamic Acid - chemical synthesis; Polylysine - chemical synthesis; Trimethylsilyl Compounds - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja803304x

We report a new strategy that uses N-trimethylsilyl (N-TMS) amine to mediate controlled ring-opening polymerization of amino acid N-carboxyanhydrides (NCAs). This polymerization proceeds via a unique, trimethylsilyl carbamate (TMS-CBM) propagating group that results from the cleavage of the Si−N bond of N-TMS amine followed by NCA ring opening. Propagation of the polypeptide chains proceeds through the transfer of the TMS group from the terminal TMS-CBM to the incoming monomer followed by the formation of a new TMS-CBM propagating group. Formation of the TMS-CBM was confirmed by MS and NMR. Polypeptides formed by the N-TMS amine-mediated polymerization have the expected molecular weights, narrow molecular weight distributions, and controlled functional groups at the C-termini of the polypeptides.