Gold-Catalyzed Aromatizations of 3-Ene-5-siloxy-1,6-diynes with Nitrosoarenes To Enable 1,4-N,O-Functionalizations: One-Pot Construction of 4-Hydroxy-3-aminobenzaldehyde Cores.

This work describes gold-catalyzed aromatizations of 3-ene-5-siloxy-1,6-diynes with nitrosoarenes to form 4-hydroxy-3-aminobenzaldehyde derivatives, manifesting the use of nitrosoarenes as 1,4-N,O-functionalization sources. Various 3-ene-5-siloxy-1,6-diynes in benzoid and nonbenzoid types are applicable substrates. A series of 18O- and 2H-labeling experiments have been conducted to exclude gold-π-alkyne intermediates. We postulate a mechanism of dual gold catalysis involving initial formation of gold-π-alkynylgold species that activates a 1,5-hydrogen shift to form reactive 1,6-dipoles, thus furnishing intramolecular Michael-type reactions with nitrosonium electrophiles.