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On the Validity of Au-vinylidenes in the Gold-Catalyzed 1,2-Migratory Cycloisomerization of Skipped Propargylpyridines

     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 -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.