Construction of α‐Pyrones and Enamine Derivatives via Divergent Transformations of β‐Aminoacrylates

A DABCO‐mediated Mannich‐type reaction of ketenimines with acylacetonitriles toward the stable β‐aminoacrylates is reported. The multifunctional properties of β‐aminoacrylates led to the discovery of a solvent‐controlled divergent access to 3,4,5,6‐tetrasubstituted α‐pyrones and enamine derivatives. In addition, the selective reduction and dihalogenation of β‐aminoacrylates are also achieved, which greatly increased the structural diversity of the products.