1. Academic Validation
  2. A strategy for sequence control in vinyl polymers via iterative controlled radical cyclization

A strategy for sequence control in vinyl polymers via iterative controlled radical cyclization

  • Nat Commun. 2016 Mar 21:7:11064. doi: 10.1038/ncomms11064.
Yusuke Hibi 1 Makoto Ouchi 1 2 Mitsuo Sawamoto 1
Affiliations

Affiliations

  • 1 Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
  • 2 Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), 4-1-8 Kawaguchi, Saitama 332-0012, Japan.
Abstract

There is a growing interest in sequence-controlled Polymers toward advanced functional Materials. However, control of side-chain order for vinyl Polymers has been lacking feasibility in the field of polymer synthesis because of the inherent feature of chain-growth propagation. Here we show a general and versatile strategy to control sequence in vinyl Polymers through iterative radical cyclization with orthogonally cleavable and renewable bonds. The proposed methodology employs a repetitive and iterative intramolecular cyclization via a radical intermediate in a one-time template with a radical-generating site at one end and an alkene end at the Other, each of which is connected to a linker via independently cleavable and renewable bonds. The unique design specifically allowed control of radical addition reaction although inherent chain-growth intermediate (radical species) was used, as well as the iterative cycle and functionalization for resultant side chains, to lead to sequence-controlled vinyl Polymers (or oligomers).

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