Gold(I)-Catalyzed Cyclization/Carbonylation Cascade Reaction of 1,6-Diynes: An Access to β,γ-Unsaturated Ketones.

A gold-catalyzed cyclization/carbonylation cascade reaction of 1,6-diynes is reported. The reaction goes through 6-exo-dig and 6-endo-dig cyclizations in sequence, followed by hydration to provide the β,γ-unsaturated ketones with moderate to high yields under mild reaction conditions. This is the first example of intercepting the postulated 1,3-oxazine vinylgold intermediate with another pendant alkyne, which not only verifies the proposed mechanism but also provides the ketone products with cyclized 1,2,3,6-tetrahydropyridine or 3,6-dihydro-2H-pyran frameworks from corresponding diynes.