Cobalt‐Catalyzed Annulation of Salicylaldehydes and Alkynes to Form Chromones and 4‐Chromanones

A unique cobalt(I)–diphosphine catalytic system has been identified for the coupling of salicylaldehyde (SA) and an internal alkyne affording a dehydrogenative annulation product (chromone) or a reductive annulation product (4‐chromanone) depending on the alkyne substituents. Distinct from related rhodium(I)‐ and rhodium(III)‐catalyzed reactions of SA and alkynes, these annulation reactions feature aldehyde C?H oxidative addition of SA and subsequent hydrometalation of the C=O bond of another SA molecule as common key steps. The reductive annulation to 4‐chromanones also involves the action of Zn as a stoichiometric reductant. In addition to these mechanistic features, the Co^I catalysis described herein is complementary to the Rh^I‐ and Rh^III‐catalyzed reactions of SA and internal alkynes, particularly in the context of chromone synthesis.