Synthesis of discrete oligomers by sequential PET-RAFT single-unit monomer insertion

Jiangtao Xu, Changkui Fu, Sivaprakash Shanmugam, Craig J. Hawker, Graeme Moad, Cyrille Boyer

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153 Citations (Scopus)


Uniform synthetic polymers with precisely defined molar mass and monomer sequence (primary structure) have many potential high-value applications. However, a robust and versatile synthetic strategy for these materials remains one of the great challenges in polymer synthesis. Herein we describe proof-of-principle experiments for a modular strategy to produce discrete oligomers by a visible-light-mediated radical chain process. We utilize the high selectivity provided by photo-induced electron/energy transfer (PET) activation to develop efficient single unit monomer insertion (SUMI) into reversible addition-fragmentation chain-transfer (RAFT) agents. A variety of discrete oligomers (single unit species, dimers, and, for the first time, trimers) have been synthesized by sequential SUMI in very high yield under mild reaction conditions. The trimers were used as building blocks for the construction of uniform hexamers and graft copolymers with precisely defined branches.

Original languageEnglish
Pages (from-to)8376-8383
Number of pages8
JournalAngewandte Chemie - International Edition
Issue number29
Publication statusPublished - 10 Jul 2017
Externally publishedYes


  • Photopolymerization
  • RAFT polymerization
  • Sequence control
  • Single unit monomer insertion

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