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Strongly Electron Deficient Sulfonyldithioformate Based RAFT Agents for Hetero Diels-Alder Conjugation: Computational Design and Experimental Evaluation

Nebhani, Leena; Sinnwell, Sebastian; Lin, Ching-Yeh; Coote, Michelle; Stenzel, Martina H; Barner-Kowollik, Christopher

Description

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)...[Show more]

dc.contributor.authorNebhani, Leena
dc.contributor.authorSinnwell, Sebastian
dc.contributor.authorLin, Ching-Yeh
dc.contributor.authorCoote, Michelle
dc.contributor.authorStenzel, Martina H
dc.contributor.authorBarner-Kowollik, Christopher
dc.date.accessioned2015-12-10T22:40:49Z
dc.identifier.issn0887-624X
dc.identifier.urihttp://hdl.handle.net/1885/57614
dc.description.abstractThe 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.
dc.publisherWiley-VCH Verlag GMBH
dc.sourceJournal of Polymer Science: Part A: Polymer Chemistry
dc.subjectKeywords: 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 r
dc.titleStrongly Electron Deficient Sulfonyldithioformate Based RAFT Agents for Hetero Diels-Alder Conjugation: Computational Design and Experimental Evaluation
dc.typeJournal article
local.description.notesImported from ARIES
local.identifier.citationvolume47
dc.date.issued2009
local.identifier.absfor030305 - Polymerisation Mechanisms
local.identifier.absfor030799 - Theoretical and Computational Chemistry not elsewhere classified
local.identifier.ariespublicationu4217927xPUB408
local.type.statusPublished Version
local.contributor.affiliationNebhani, Leena, Universitat Karlsruhe
local.contributor.affiliationSinnwell, Sebastian, Universitat Karlsruhe
local.contributor.affiliationLin, Ching-Yeh, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationCoote, Michelle, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationStenzel, Martina H, University of New South Wales
local.contributor.affiliationBarner-Kowollik, Christopher, University of New South Wales
local.description.embargo2037-12-31
local.bibliographicCitation.issue22
local.bibliographicCitation.startpage6053
local.bibliographicCitation.lastpage6071
local.identifier.doi10.1002/pola.23647
local.identifier.absseo970103 - Expanding Knowledge in the Chemical Sciences
dc.date.updated2016-02-24T10:43:07Z
local.identifier.scopusID2-s2.0-70350236398
local.identifier.thomsonID000271670000012
CollectionsANU Research Publications

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