1,3-Dipolar cycloaddition of organic azides to alkynes by a dicopper-substituted silicotungstate

Keigo Kamata, Yoshinao Nakagawa, Kazuya Yamaguchi, Noritaka Mizuno

Research output: Contribution to journalArticlepeer-review

149 Citations (Scopus)

Abstract

The dicopper-substituted γ-Keggin silicotungstate TBA 4[γ-H2SiW10O36Cu 2(μ-1,1-N3)2] (I, TBA = tetra-n- butylammonium) could act as an efficient precatalyst for the regioselective 1,3-dipolar cycloaddition of organic azides to alkynes. Various combinations of substrates (four azides and eight alkynes) were efficiently converted to the corresponding 1,2,3-triazole derivatives in excellent yields without any additives. The present system was applicable to a larger-scale cycloaddition of benzyl azide to phenylacetylene under solvent-free conditions (100 mmol scale) in which 21.5 g of the analytically pure corresponding triazole could be isolated. In this case, the turnover frequency and the turnover number reached up to 14 800 h-1 and 91 500, respectively, and these values were the highest among those reported for the copper-mediated systems so far. In addition, I could be applied to the one-pot synthesis of 1-benzyl-4-phenyl-1H-1, 2,3-triazole from benzyl chloride, sodium azide, and phenylacetylene. The catalyst effect, kinetic, mechanistic, and computational studies show that the reduced dicopper core plays an important role in the present 1,3-dipolar cycloaddition.

Original languageEnglish
Pages (from-to)15304-15310
Number of pages7
JournalJournal of the American Chemical Society
Volume130
Issue number46
DOIs
Publication statusPublished - 2008 Nov 19
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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