Scope and reaction mechanism of an aerobic oxidative alkyne homocoupling catalyzed by a di-copper-substituted silicotungstate

Noritaka Mizuno, Keigo Kamata, Yoshinao Nakagawa, Takamichi Oishi, Kazuya Yamaguchi

Research output: Contribution to journalArticlepeer-review

25 Citations (Scopus)

Abstract

The di-copper-substituted γ-Keggin-type silicotungstate TBA 4[γ-H2SiW10O36Cu 2(μ-1,1-N3)2] (I, TBA = tetra-n- butylammonium) could act as an efficient reusable homogeneous catalyst for the aerobic oxidative alkyne homocoupling. Various kinds of structurally diverse terminal alkynes including aromatic, heteroaromatic, aliphatic, double bond-containing, silylacetylene, propargylic alcohol, and propargylic amine derivatives could selectively be converted into the corresponding diynes in the presence of I. The catalytic activity of I was much higher than those of the mono-copper-substituted silicotungstate, monomeric copper complexes, and simple copper salts, showing that the di-copper core in I plays an important role in the present alkyne homocoupling. The reaction mechanism involving the formation of the di-copper(II)-alkynyl intermediate, reductive elimination of a diyne, and re-oxidation of reduced copper species by O2 has been proposed.

Original languageEnglish
Pages (from-to)359-363
Number of pages5
JournalCatalysis Today
Volume157
Issue number1-4
DOIs
Publication statusPublished - 2010 Nov 17
Externally publishedYes

Keywords

  • Alkyne
  • Copper
  • Homocoupling
  • Molecular oxygen
  • Polyoxometalate

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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