Title |
A strategy for sequence control in vinyl polymers via iterative controlled radical cyclization
|
---|---|
Published in |
Nature Communications, March 2016
|
DOI | 10.1038/ncomms11064 |
Pubmed ID | |
Authors |
Yusuke Hibi, Makoto Ouchi, Mitsuo Sawamoto |
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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