Dehydrogenative Meyer-Schuster-Like Rearrangement: A Gold-Catalyzed Reaction Generating an Alkyne

Easily accessible propargylic esters are converted to the inverted alkynyl ketones in an oxidative gold-catalyzed reaction. Gagosz's catalyst in combination with PhI(OAc)(2) is the best system for this conversion and 18 examples with yields up to 80% are reported. The results indicate that the triple bond in the product is formed by elimination from a vinylgold intermediate. In a formal sense the new conversion overall is a dehydrogenative Meyer-Schuster rearrangement.