Modulating two copper(I)-catalyzed orthogonal "click" reactions for the one-pot synthesis of highly branched polymer architectures at 25 °c

Bell, Craig A., Jia, Zhongfan, Kulis, Jakov and Monteiro, Michael J. (2011) Modulating two copper(I)-catalyzed orthogonal "click" reactions for the one-pot synthesis of highly branched polymer architectures at 25 °c. Macromolecules, 44 12: 4814-4827. doi:10.1021/ma200649b


Author Bell, Craig A.
Jia, Zhongfan
Kulis, Jakov
Monteiro, Michael J.
Title Modulating two copper(I)-catalyzed orthogonal "click" reactions for the one-pot synthesis of highly branched polymer architectures at 25 °c
Journal name Macromolecules   Check publisher's open access policy
ISSN 0024-9297
1520-5835
Publication date 2011-06
Sub-type Article (original research)
DOI 10.1021/ma200649b
Volume 44
Issue 12
Start page 4814
End page 4827
Total pages 14
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2012
Language eng
Formatted abstract
Controlling the rates of orthogonal "click" reactions in one-pot provides a method for designing highly branched macromolecular architectures. In this work, we constructed third generation (G3) dendrimers consisting of a wide range of chemically different polymer building blocks in one pot at 25 °C. This approach reduced the number of purification and chemical protection steps. Using the model polystyrene (PSTY) building block system, third generation dendrimers could be formed divergently, convergently or in parallel through modulating the Cu(I) activity for the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and nitroxide radical coupling (NRC) reactions. The parallel approach was the fastest, generating a G3 dendrimer in under 30 min, and the next fastest was the divergent pathway, followed by the very slow (24 h) convergent pathway. The resulting G3 dendrimer could be cleaved at the alkoxyamine sites back to linear polymers by heating the reaction mixture at 120 °C in the presence of an excess hydroxyl nitroxide. The synthetic utility of this method was further extended to coupling linear telechelic polymer building blocks, consisting of PSTY, PtBA, PEG, and PNIPAM, to form a range of dendrimers in high yields. Preparative SEC was used to fractionate excess starting reactants and intermediate polymer species from the product dendrimer.
Keyword Alkoxyamines
Azide-alkyne cycloaddition
Transfer radical polymerization
Selective degradable linkages
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2012 Collection
Australian Institute for Bioengineering and Nanotechnology Publications
 
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Created: Wed, 19 Oct 2011, 14:00:00 EST by Dr Zhongfan Jia on behalf of Aust Institute for Bioengineering & Nanotechnology