Phenyl Trimethylsilyl Sulfide-Mediated Controlled Ring-Opening Polymerization of α-Amino Acid N-Carboxyanhydrides

Biomacromolecules
Jingsong YuanHua Lu

Abstract

We describe here the first example of trimethylsilyl sulfide (S-TMS) mediated controlled ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCAs). We show that phenyl trimethylsilyl sulfide (PhS-TMS), an inexpensive and commercially available compound, mediates rapid ROP of a broad scope of NCA monomers, produces functional poly(amino acids) (PAAs) with controllable molecular weights (MWs), narrow polydispersity index (PDI), and an in situ generated phenyl thioester group at the C-terminus (PAA-SPhs). PhS-TMS offers more rapid chain initiation than previously reported hexamethyldisilazane (HMDS) initiator, ensuring a living polymerization with better control. Mechanistic studies suggest that a reactive trimethylsilyl carbamate (TMSC) was generated during the chain initiation and continued to regulate the chain propagation through a TMS transfer process. Considering the versatility of NCAs, and the potential of leveraging the C-terminal phenyl thioester for native chemical ligation (NCL), we believe this method may offer a powerful platform enabling the rapid generation of functional PAAs and their C-terminal conjugates for numerous biological applications.

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Citations

May 20, 2017·The Journal of Physical Chemistry. a·Tianwen Bai, Jun Ling
Oct 25, 2017·Polymers·Carmen M González-HenríquezJuan Rodríguez-Hernández
Mar 29, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Yanzhao NieJing Yang
Jul 21, 2020·Biomacromolecules·Karoline E EckhartStefanie A Sydlik
Jun 5, 2018·Bioconjugate Chemistry·Yali HuHua Lu
May 3, 2019·Bioconjugate Chemistry·Yingqin Hou, Hua Lu
Sep 26, 2021·Macromolecular Rapid Communications·Botuo ZhengJun Ling

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