The first gold-catalyzed direct intermolecular coupling of ketones, secondary amines, and alkynes was achieved under mild and solvent-free conditions. The present methodology provides a promising and versatile tool for the construction of propargylic amines with a newly-formed quaternary carbon center.

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Direct access: The title reaction has been developed under mild reaction conditions (see scheme; DMSO=dimethyl sulfoxide). This reaction can be effectively scaled up and offers not only a green and attractive approach to β‐ketophosphonates, but also a useful example of direct incorporation of an oxygen atom from dioxygen into organic frameworks.