On the validity of au-vinylidenes in the gold-catalyzed 1,2-migratory cycloisomerization of skipped propargylpyridines

Yuanzhi Xia, Alexander S. Dudnik, Yahong Li, Vladimir Gevorgyan

Research output: Contribution to journalArticle

75 Citations (Scopus)

Abstract

A mechanism of the Au-catalyzed cycloisomerization of propargylpyridines has been investigated. Both DFT computational and experimental results strongly support generation of a Au-carbene via a cyclization/proton transfer sequence over the previously proposed path involving a Au-vinylidene intermediate. For the β-Si-substituted Au-carbene (G = SiR3), a 1,2-Si migration was shown to be kinetically favored over a 1,2-H shift. This study highlights the importance of alternative pathways that could explain reactivities commonly attributed to an alkyne-vinylidene isomerization in Au catalysis.

Original languageEnglish (US)
Pages (from-to)5538-5541
Number of pages4
JournalOrganic Letters
Volume12
Issue number23
DOIs
StatePublished - Dec 3 2010
Externally publishedYes

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carbenes
vinylidene
Gold
gold
Proton transfer
Alkynes
Cyclization
alkynes
Isomerization
Catalysis
Discrete Fourier transforms
isomerization
catalysis
Protons
reactivity
protons
shift
carbene

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

On the validity of au-vinylidenes in the gold-catalyzed 1,2-migratory cycloisomerization of skipped propargylpyridines. / Xia, Yuanzhi; Dudnik, Alexander S.; Li, Yahong; Gevorgyan, Vladimir.

In: Organic Letters, Vol. 12, No. 23, 03.12.2010, p. 5538-5541.

Research output: Contribution to journalArticle

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AU - Gevorgyan, Vladimir

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