Radical-promoted single-unit monomer insertion (SUMI) [aka. reversible-deactivation radical addition (RDRA)]

We survey progress in the development of the processes for radical-promoted single-unit monomer insertion (SUMI) or reversible deactivation radical addition (RDRA), focussing on aminoxyl- [nitroxide-] mediated SUMI (NM-SUMI), reversible-addition-fragmentation chain transfer-SUMI (RAFT-SUMI) and atom...

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Bibliographic Details
Published in:Progress in polymer science 2023-03, Vol.138, p.101648, Article 101648
Main Authors: Boyer, Cyrille, Kamigaito, Masami, Satoh, Kotaro, Moad, Graeme
Format: Article
Language:English
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Summary:We survey progress in the development of the processes for radical-promoted single-unit monomer insertion (SUMI) or reversible deactivation radical addition (RDRA), focussing on aminoxyl- [nitroxide-] mediated SUMI (NM-SUMI), reversible-addition-fragmentation chain transfer-SUMI (RAFT-SUMI) and atom-transfer radical addition (ATRA). Radical-promoted thiol-ene processes are also briefly discussed. We detail the strategies for achieving selectivity with respect to single unit insertion vs oligomerization and look critically at progress towards discrete oligomer synthesis by consecutive SUMI reactions. We examine the use of SUMI to install α-, ω- or mid-chain-functionality in RDRP-synthesized polymers. Finally, we examine the prospects for using radical-promoted SUMI in the synthesis of sequence-defined polymers where monomer placement is precisely defined to the level of the individual monomer units in the polymer chain. [Display omitted]
ISSN:0079-6700
1873-1619
DOI:10.1016/j.progpolymsci.2023.101648