Ruthenium-catalyzed azide-alkyne cycloaddition

Scope and mechanism

Brant C. Boren, Sridhar Narayan, Lars K. Rasmussen, Li Zhang, Haitao Zhao, Zhenyang Lin, Guochen Jia, Valery V. Fokin

Research output: Contribution to journalArticle

522 Citations (Scopus)

Abstract

The catalytic activity of a series of ruthenium(II) complexes in azide-alkyne cycloadditions has been evaluated. The [Cp*RuCl] complexes, such as Cp*RuCl(PPh3)2, Cp*RuCI(COD), and Cp*RuCl(NBD), were among the most effective catalysts. In the presence of catalytic Cp*RuCI(PPh3)2 or Cp*RuCl(COD), primary and secondary azides react with a broad range of terminal alkynes containing a range of functionalities selectively producing 1,5-disubstituted 1,2,3-triazoles; tertiary azides were significantly less reactive. Both complexes also promote the cycloaddition reactions of organic azides with internal alkynes, providing access to fully-substituted 1,2,3-triazoles. The ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) appears to proceed via oxidative coupling of the azide and alkyne reactants to give a six-membered ruthenacycle intermediate, in which the first new carbon-nitrogen bond is formed between the more electronegative carbon of the alkyne and the terminal, electrophilic nitrogen of the azide. This step is followed by reductive elimination, which forms the triazole product. DFT calculations support this mechanistic proposal and indicate that the reductive elimination step is rate-determining.

Original languageEnglish
Pages (from-to)8923-8930
Number of pages8
JournalJournal of the American Chemical Society
Volume130
Issue number28
DOIs
Publication statusPublished - 16 Jul 2008
Externally publishedYes

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Alkynes
Ruthenium
Azides
Cycloaddition
Cycloaddition Reaction
Triazoles
Nitrogen
Carbon
Discrete Fourier transforms
Catalyst activity
Oxidative Coupling
Catalysts

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Boren, B. C., Narayan, S., Rasmussen, L. K., Zhang, L., Zhao, H., Lin, Z., ... Fokin, V. V. (2008). Ruthenium-catalyzed azide-alkyne cycloaddition: Scope and mechanism. Journal of the American Chemical Society, 130(28), 8923-8930. https://doi.org/10.1021/ja0749993

Ruthenium-catalyzed azide-alkyne cycloaddition : Scope and mechanism. / Boren, Brant C.; Narayan, Sridhar; Rasmussen, Lars K.; Zhang, Li; Zhao, Haitao; Lin, Zhenyang; Jia, Guochen; Fokin, Valery V.

In: Journal of the American Chemical Society, Vol. 130, No. 28, 16.07.2008, p. 8923-8930.

Research output: Contribution to journalArticle

Boren, BC, Narayan, S, Rasmussen, LK, Zhang, L, Zhao, H, Lin, Z, Jia, G & Fokin, VV 2008, 'Ruthenium-catalyzed azide-alkyne cycloaddition: Scope and mechanism', Journal of the American Chemical Society, vol. 130, no. 28, pp. 8923-8930. https://doi.org/10.1021/ja0749993
Boren BC, Narayan S, Rasmussen LK, Zhang L, Zhao H, Lin Z et al. Ruthenium-catalyzed azide-alkyne cycloaddition: Scope and mechanism. Journal of the American Chemical Society. 2008 Jul 16;130(28):8923-8930. https://doi.org/10.1021/ja0749993
Boren, Brant C. ; Narayan, Sridhar ; Rasmussen, Lars K. ; Zhang, Li ; Zhao, Haitao ; Lin, Zhenyang ; Jia, Guochen ; Fokin, Valery V. / Ruthenium-catalyzed azide-alkyne cycloaddition : Scope and mechanism. In: Journal of the American Chemical Society. 2008 ; Vol. 130, No. 28. pp. 8923-8930.
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