Strongly electron deficient sulfonyldithioformate based raft agents for hetero diels-alder conjugation: Computational design and experimental evaluation

Nebhani, L., Sinnwell, S., Lin, C. Y., Coote, M. L., Stenzel, M. H., & Barner-Kowollik, C. (2009) Strongly electron deficient sulfonyldithioformate based raft agents for hetero diels-alder conjugation: Computational design and experimental evaluation. Journal of Polymer Science, Part A: Polymer Chemistry, 47(22).

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Abstract

The synthesis of a novel class of reversible addition-fragmentation chain transfer (RAFT) agents-based on quantum-chemical ab initio calculations-having methylsulfonyl and phenylsulfonyl moieties as Z-group is described. The resulting C-sulfonyldithioformate transfer agents [benzyl methylsulfonyldithioformate (PSDTF) and benzyl phenylsulfonyldithioformate (PSDTF)] feature extremely strong electron deficient C=S double bonds and should thus be suitable to undergo rapid hetero Diels-Alder (HDA) reactions with variable dienes under mild (i.e., ambient and catalyst free) reaction conditions. It can be demonstrated via a series of model reactions, whose outcome is monitored via electrospray ionization mass spectrometry (ESI-MS), that C-sulfonyldithioformate based RAFT agents undergo HDA reactions with a series of diene-capped macromolecules (10 min\ reaction time\ 24 h) at ambient temperatures (T ≈25°C) with reaction times ranging from 24 h (for open chain dienes) to a few minutes (for cyclopentadiene) in the absence of any catalysts. Concomitantly, PSDTF is able to efficiently mediate the polymerization of isobornyl acrylate (iBA) with living characteristics (2300\ Mn (g/mol)\ 16,000, 1.08\ PDI \ 1.31). In a subsequent step, it is demonstrated that conjugates of poly(iBA) and polystyrene can be constructed under mild reaction conditions (reaction time \ 10 min, T ≈25°C, Mn≈ 6000 (g/mol), PDI≈1.3, no catalyst). In addition, we highlight that sulfonyldithioformate type RAFT agents are such effective dienophiles that they can undergo HDA reactions with certain monomers, including styrene. While such a strong HDA activity limits their use in polymerizations, it opens an avenue for catalyst free efficient surface modification reactions under mild conditions with variable dienes. © 2009 Wiley Periodicals, Inc.

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ID Code: 99225
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :35
Export Date: 5 September 2016
CODEN: JPACE
Correspondence Address: Coote, M. L.; ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia; email: mcoote@rsc.anu.edu.au
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Keywords: Ab initio calculations, Ambient temperatures, Catalyst-free, Computational design, Cyclopentadienes, Dienophiles, Double bonds, Efficient surface, Electron-deficient, Electrospray ionization mass spectrometry, Experimental evaluation, Hetero-diels, Mild reaction conditions, Model reactions, Open chain, RAFT agents, Reaction conditions, Reaction time, Reversible addition-fragmentation chain transfer, Transfer agents, Catalysis, Catalysts, Chemical bonds, Directive antennas, Electrospray ionization, Face recognition, Free radical polymerization, Human reaction time, Living polymerization, Manganese, Manganese compounds, Mass spectrometry, Olefins, Polystyrenes, Styrene, Supramolecular chemistry, Surface reactions
DOI: 10.1002/pola.23647
ISSN: 0887624X
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 07 Oct 2016 04:30

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