skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions

Abstract

Functional polystyrenes and polyacrylamides, containing combinations of fluorosulfate, aromatic silyl ether, and azide side chains, were used as scaffolds to demonstrate the postpolymerization modification capabilities of sulfur(VI) fluoride exchange (SuFEx) and CuAAC chemistries. Fluorescent dyes bearing appropriate functional groups were sequentially attached to the backbone of the copolymers, quantitatively and selectively addressing their reactive partners. Furthermore, this combined SuFEx and CuAAC approach proved to be robust and versatile, allowing for a rare accomplishment: triple orthogonal functionalization of a copolymer under essentially ambient conditions without protecting groups.

Authors:
 [1];  [1];  [1]
  1. Univ. of Southern California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1411674
Report Number(s):
LLNL-JRNL-736721
Journal ID: ISSN 0024-9297; TRN: US1800271
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 49; Journal Issue: 12; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Oakdale, James S., Kwisnek, Luke, and Fokin, Valery V. Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions. United States: N. p., 2016. Web. doi:10.1021/acs.macromol.6b00101.
Oakdale, James S., Kwisnek, Luke, & Fokin, Valery V. Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions. United States. doi:10.1021/acs.macromol.6b00101.
Oakdale, James S., Kwisnek, Luke, and Fokin, Valery V. Fri . "Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions". United States. doi:10.1021/acs.macromol.6b00101. https://www.osti.gov/servlets/purl/1411674.
@article{osti_1411674,
title = {Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions},
author = {Oakdale, James S. and Kwisnek, Luke and Fokin, Valery V.},
abstractNote = {Functional polystyrenes and polyacrylamides, containing combinations of fluorosulfate, aromatic silyl ether, and azide side chains, were used as scaffolds to demonstrate the postpolymerization modification capabilities of sulfur(VI) fluoride exchange (SuFEx) and CuAAC chemistries. Fluorescent dyes bearing appropriate functional groups were sequentially attached to the backbone of the copolymers, quantitatively and selectively addressing their reactive partners. Furthermore, this combined SuFEx and CuAAC approach proved to be robust and versatile, allowing for a rare accomplishment: triple orthogonal functionalization of a copolymer under essentially ambient conditions without protecting groups.},
doi = {10.1021/acs.macromol.6b00101},
journal = {Macromolecules},
number = 12,
volume = 49,
place = {United States},
year = {2016},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 37 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

A Heck-Matsuda Process for the Synthesis of β-Arylethenesulfonyl Fluorides: Selectively Addressable Bis-electrophiles for SuFEx Click Chemistry
journal, October 2016

  • Qin, Hua-Li; Zheng, Qinheng; Bare, Grant A. L.
  • Angewandte Chemie International Edition, Vol. 55, Issue 45
  • DOI: 10.1002/anie.201608807

A New Portal to SuFEx Click Chemistry: A Stable Fluorosulfuryl Imidazolium Salt Emerging as an “F−SO 2 +” Donor of Unprecedented Reactivity, Selectivity, and Scope
journal, January 2018

  • Guo, Taijie; Meng, Genyi; Zhan, Xiongjie
  • Angewandte Chemie International Edition, Vol. 57, Issue 10
  • DOI: 10.1002/anie.201712429

1-Bromoethene-1-sulfonyl fluoride (BESF) is another good connective hub for SuFEx click chemistry
journal, January 2018

  • Smedley, Christopher J.; Giel, Marie-Claire; Molino, Andrew
  • Chemical Communications, Vol. 54, Issue 47
  • DOI: 10.1039/c8cc03400a

Site-selective conversion of azido groups at carbonyl α-positions into oxime groups leading triazide to a triple click conjugation scaffold
journal, January 2019

  • Yokoi, Taiki; Ueda, Tomomi; Tanimoto, Hiroki
  • Chemical Communications, Vol. 55, Issue 13
  • DOI: 10.1039/c8cc09415b

A Heck-Matsuda Process for the Synthesis of β-Arylethenesulfonyl Fluorides: Selectively Addressable Bis-electrophiles for SuFEx Click Chemistry
journal, October 2016

  • Qin, Hua-Li; Zheng, Qinheng; Bare, Grant A. L.
  • Angewandte Chemie International Edition, Vol. 55, Issue 45
  • DOI: 10.1002/anie.201608807

1-Bromoethene-1-sulfonyl fluoride (BESF) is another good connective hub for SuFEx click chemistry
journal, January 2018

  • Smedley, Christopher J.; Giel, Marie-Claire; Molino, Andrew
  • Chemical Communications, Vol. 54, Issue 47
  • DOI: 10.1039/c8cc03400a

Site-selective conversion of azido groups at carbonyl α-positions into oxime groups leading triazide to a triple click conjugation scaffold
journal, January 2019

  • Yokoi, Taiki; Ueda, Tomomi; Tanimoto, Hiroki
  • Chemical Communications, Vol. 55, Issue 13
  • DOI: 10.1039/c8cc09415b