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 language | English (US) |
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Pages (from-to) | 5538-5541 |
Number of pages | 4 |
Journal | Organic Letters |
Volume | 12 |
Issue number | 23 |
DOIs | |
State | Published - Dec 3 2010 |
Externally published | Yes |
ASJC Scopus subject areas
- Biochemistry
- Physical and Theoretical Chemistry
- Organic Chemistry