The Radical Chemistry of Thiocarbonylthio Compounds: An Overview

Abstract

International audienc

Characterization and electrical properties of methyl‐2‐hydroxyethyl cellulose doped with erbium nitrate salt

“…The mechanism of MADIX/RAFT polymerization was established by Zard and coworkers15–20 and by Rizzardo and coworkers21–25 in the late 1990s, and whilst there still seems to be some intrigue over aspects of the mechanism under specific conditions,26–28 we contend that 99% of the story is known22, 29 and certainly enough to establish RAFT as a powerful synthetic technique for making a wide range of complex architectures including stars, combs, blocks and brushes 30. The CSIRO team has continued to monitor and report on the progress of RAFT technology through a series of reviews in the Australian Journal of Chemistry 22–23, 31 and through the RAFT alliance 32.…”

RAFT Polymerization and Thiol Chemistry: A Complementary Pairing for Implementing Modern Macromolecular Design

“…In the context of this review it is important to note that thiols are routinely employed in the synthesis of thiocarbonylthio compounds, such as xanthates, dithiocarbamates, dithioesters, and trithiocarbonates. Initially, such compounds were developed by Zard and coworkers [6] for radical reactions in organic synthesis. Similar compounds were subsequently used as CTAs by Rizzardo, Moad, and Thang in polymer synthesis, viz, reversible addition fragmentation chain transfer (RAFT) polymerization [7][8][9][10] or macromolecular design via interchange of xanthates (MADIX).…”

Building nanostructures using RAFT polymerization

“…In very recent research, programs have also been established to study compartmentalization in heterogeneous polymerizations, 12 and macromolecular design using thiolene 13 and thiol-yne chemistry. 14 The mechanism of MADIX/RAFT polymerization was established by Zard and coworkers [15][16][17][18][19][20] and by Rizzardo and coworkers [21][22][23][24][25] in the late 1990s, and whilst there still seems to be some intrigue over aspects of the mechanism under specific conditions, [26][27][28] we contend that 99% of the story is known 22,29 and certainly enough to establish RAFT as a powerful synthetic technique for making a wide range of complex architectures including stars, combs, blocks and brushes. 30 The CSIRO team has continued to monitor and report on the progress of RAFT technology through a series of reviews in the Australian Journal of Chemistry [22][23]31 and through the RAFT alliance.…”

“…At low conversion, the formation of linear polymer is observed, while at relatively high conversion (90), the formation of hyperbranched polymers is achieved, for very high conversion, the formation of gel is observed. successfully imaged in vivo using 19 F MRI. These hyperbranched polymers are obtained by copolymerization of dimethylaminoethylacrylate (DMAEA, 77 mol %) and trifluoroethyl acrylate cytocompatible (23 mol %), following chain extension with PEGMA in the presence of alkyne functionalized trithiocarbonate.…”

“…The presence of alkyne end group allows the attachment of azide mannose. These functional hyperbranched are cytocompatible and can be successfully imaged in vivo using 19 F MRI in under 10 min.…”