Lewis acid catalyzed trans-allylsilylation of unactivated alkynes

Eiji Yoshikawa, Vladimir Gevorgyan, Naoki Asao, Yoshinori Yamamoto

Research output: Contribution to journalArticle

84 Citations (Scopus)

Abstract

The addition of different substituted allylsilanes 2 to unactivated alkynes 1 in the presence of catalytic mounts of HfCl4 or the EtAlCl2- TMSC1 catalyst system produced in high yields the silylated 1,4-dienes 3 regio- and stereoselectively. The exclusive trans manner of addition was confirmed by analysis of crude reaction mixtures by 1H NMR and capillary GLC methods. Good agreement of relative reactivities of reaction of various allylsilanes 2a-e toward phenylacetylene (1a) in the presence of HfCl4 with the relative reaction rates of 2a-e with carbenium ions supported the involvement of cationic species 11 as a reaction intermediate. The mechanisms for the HfCl4 and EtAlCl2-TMS catalyzed trans-allylsilylation of alkynes are proposed.

Original languageEnglish (US)
Pages (from-to)6781-6786
Number of pages6
JournalJournal of the American Chemical Society
Volume119
Issue number29
DOIs
StatePublished - Jul 23 1997
Externally publishedYes

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Lewis Acids
Reaction intermediates
Alkynes
Reaction rates
Nuclear magnetic resonance
Catalysts
Acids
Ions
allylsilane
dichloroethylaluminum
phenylacetylene
Proton Magnetic Resonance Spectroscopy

ASJC Scopus subject areas

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

Cite this

Lewis acid catalyzed trans-allylsilylation of unactivated alkynes. / Yoshikawa, Eiji; Gevorgyan, Vladimir; Asao, Naoki; Yamamoto, Yoshinori.

In: Journal of the American Chemical Society, Vol. 119, No. 29, 23.07.1997, p. 6781-6786.

Research output: Contribution to journalArticle

Yoshikawa, Eiji ; Gevorgyan, Vladimir ; Asao, Naoki ; Yamamoto, Yoshinori. / Lewis acid catalyzed trans-allylsilylation of unactivated alkynes. In: Journal of the American Chemical Society. 1997 ; Vol. 119, No. 29. pp. 6781-6786.
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