Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion

Zixuan Huang, Benjamin B. Noble, Nathaniel Corrigan, Yingying Chu, Kotaro Satoh, Donald S. Thomas, Craig J. Hawker, Graeme Moad, Masami Kamigaito, Michelle L. Coote, Cyrille Boyer, Jiangtao Xu

Research output: Contribution to journalArticlepeer-review

69 Citations (Scopus)

Abstract

Natural biopolymers, such as DNA and proteins, have uniform microstructures with defined molecular weight, precise monomer sequence, and stereoregularity along the polymer main chain that affords them unique biological functions. To reproduce such structurally perfect polymers and understand the mechanism of specific functions through chemical approaches, researchers have proposed using synthetic polymers as an alternative due to their broad chemical diversity and relatively simple manipulation. Herein, we report a new methodology to prepare sequence-controlled and stereospecific oligomers using alternating radical chain growth and sequential photoinduced RAFT single unit monomer insertion (photo-RAFT SUMI). Two families of cyclic monomers, the indenes and the N-substituted maleimides, can be alternatively inserted into RAFT agents, one unit at a time, allowing the monomer sequence to be controlled through sequential and alternating monomer addition. Importantly, the stereochemistry of cyclic monomer insertion into the RAFT agents is found to be trans-selective along the main chains due to steric hindrance from the repeating monomer units. All investigated cyclic monomers provide such trans-selectivity, but analogous acyclic monomers give a mixed cis- and trans-insertion.

Original languageEnglish
Pages (from-to)13392-13406
Number of pages15
JournalJournal of The American Chemical Society
Volume140
Issue number41
DOIs
Publication statusPublished - 17 Oct 2018
Externally publishedYes

Keywords

  • RAFT polymerization
  • Adducts
  • Monomers
  • Oligomers
  • Molecular structure

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