title: Beyond Traditional RAFT: Alternative Activation of Thiocarbonylthio Compounds for Controlled Polymerization.
abstract: Recent developments in polymerization reactions utilizing thiocarbonylthio compounds have highlighted the surprising versatility of these unique molecules. The increasing popularity of reversible addition-fragmentation chain transfer (RAFT) radical polymerization as a means of producing well-defined, 'controlled' synthetic polymers is largely due to its simplicity of implementation and the availability of a wide range of compatible reagents. However, novel modes of thiocarbonylthio activation can expand the technique beyond the traditional system (i.e., employing a free radical initiator) pushing the applicability and use of thiocarbonylthio compounds even further than previously assumed. The primary advances seen in recent years are a revival in the direct photoactivation of thiocarbonylthio compounds, their activation via photoredox catalysis, and their use in cationic polymerizations. These synthetic approaches and their implications for the synthesis of controlled polymers represent a significant advance in polymer science, with potentially unforeseen benefits and possibilities for further developments still ahead. This Research News aims to highlight key works in this area while also clarifying the differences and similarities of each system.
authors.affiliation: Polymer Science Group Department of Chemical and Biomolecular Engineering The University of Melbourne Parkville VIC 3010 Australia.
authors.forename: Thomas G
authors.initials: TG
authors.lastname: McKenzie
authors.affiliation: Polymer Science Group Department of Chemical and Biomolecular Engineering The University of Melbourne Parkville VIC 3010 Australia.
authors.forename: Qiang
authors.initials: Q
authors.lastname: Fu
authors.affiliation: Department of Applied Chemistry Graduate School of Engineering Nagoya University Furo-cho, Chikusa-ku Nagoya 464-8603 Japan.
authors.forename: Mineto
authors.initials: M
authors.lastname: Uchiyama
authors.affiliation: Department of Applied ChemistryGraduate School of EngineeringNagoya UniversityFuro-cho, Chikusa-kuNagoya464-8603Japan; Precursory Research for Embryonic Science and TechnologyJapan Science and Technology Agency4-1-8 HonchoKawaguchi, Saitama332-0012Japan.
authors.forename: Kotaro
authors.initials: K
authors.lastname: Satoh
authors.affiliation: Center for Advanced Macromolecular Design (CAMD) and Australian Center for NanoMedicine (ACN) School of Chemical Engineering, UNSW Sydney NSW 2052 Australia.
authors.forename: Jiangtao
authors.initials: J
authors.lastname: Xu
authors.affiliation: Center for Advanced Macromolecular Design (CAMD) and Australian Center for NanoMedicine (ACN) School of Chemical Engineering, UNSW Sydney NSW 2052 Australia.
authors.forename: Cyrille
authors.initials: C
authors.lastname: Boyer
authors.affiliation: Department of Applied Chemistry Graduate School of Engineering Nagoya University Furo-cho, Chikusa-ku Nagoya 464-8603 Japan.
authors.forename: Masami
authors.initials: M
authors.lastname: Kamigaito
authors.affiliation: Polymer Science Group Department of Chemical and Biomolecular Engineering The University of Melbourne Parkville VIC 3010 Australia.
authors.forename: Greg G
authors.initials: GG
authors.lastname: Qiao
keywords: controlled/living polymerization; photochemistry; polymer structures; reversible addition‐fragmentation chain transfer (RAFT); thiocarbonyl chemistry