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Title: Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)

This report outlines the investigation of the iClick mechanism between gold(I)-azides and gold(I)-acetylides to yield digold triazolates. Isolation of digold triazolate complexes offer compelling support for the role of two copper(I) ions in CuAAC. In addition, a kinetic investigation reveals the reaction is first order in both Au(I)-N 3 and Au(I)-C≡C-R equivalent to C-R, thus second order overall. A Hammett plot with a ρ = 1.02(5) signifies electron-withdrawing groups accelerate the cycloaddition by facilitating the coordination of the second gold ion in a π-complex. Rate inhibition by the addition of free triphenylphosphine to the reaction indicates that ligand dissociation is a prerequisite for the reaction. The mechanistic conclusions mirror those proposed for the CuAAC reaction.
Authors:
 [1] ;  [1] ;  [1] ;  [1]
  1. Univ. of Florida, Gainesville, FL (United States)
Publication Date:
Grant/Contract Number:
SC0010510
Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 44; Journal Issue: 33; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Research Org:
Univ. of Florida, Gainesville, FL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1225600

Powers, Andrew R., Ghiviriga, Ion, Abboud, Khalil A., and Veige, Adam S.. Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC). United States: N. p., Web. doi:10.1039/c5dt02405f.
Powers, Andrew R., Ghiviriga, Ion, Abboud, Khalil A., & Veige, Adam S.. Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC). United States. doi:10.1039/c5dt02405f.
Powers, Andrew R., Ghiviriga, Ion, Abboud, Khalil A., and Veige, Adam S.. 2015. "Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)". United States. doi:10.1039/c5dt02405f. https://www.osti.gov/servlets/purl/1225600.
@article{osti_1225600,
title = {Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)},
author = {Powers, Andrew R. and Ghiviriga, Ion and Abboud, Khalil A. and Veige, Adam S.},
abstractNote = {This report outlines the investigation of the iClick mechanism between gold(I)-azides and gold(I)-acetylides to yield digold triazolates. Isolation of digold triazolate complexes offer compelling support for the role of two copper(I) ions in CuAAC. In addition, a kinetic investigation reveals the reaction is first order in both Au(I)-N3 and Au(I)-C≡C-R equivalent to C-R, thus second order overall. A Hammett plot with a ρ = 1.02(5) signifies electron-withdrawing groups accelerate the cycloaddition by facilitating the coordination of the second gold ion in a π-complex. Rate inhibition by the addition of free triphenylphosphine to the reaction indicates that ligand dissociation is a prerequisite for the reaction. The mechanistic conclusions mirror those proposed for the CuAAC reaction.},
doi = {10.1039/c5dt02405f},
journal = {Dalton Transactions},
number = 33,
volume = 44,
place = {United States},
year = {2015},
month = {7}
}

Works referenced in this record:

Click Chemistry: Diverse Chemical Function from a Few Good Reactions
journal, June 2001

Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis
journal, June 1977

A Stepwise Huisgen Cycloaddition Process: Copper(I)-Catalyzed Regioselective “Ligation” of Azides and Terminal Alkynes
journal, July 2002

Peptidotriazoles on Solid Phase  [1,2,3]-Triazoles by Regiospecific Copper(I)-Catalyzed 1,3-Dipolar Cycloadditions of Terminal Alkynes to Azides
journal, May 2002
  • Tornøe, Christian W.; Christensen, Caspar; Meldal, Morten
  • The Journal of Organic Chemistry, Vol. 67, Issue 9, p. 3057-3064
  • DOI: 10.1021/jo011148j