Catalyst‐free Sequential Wolff Rearrangement and [3+3] Annulation of Enaminones and Diazo compounds Enabling the Assembly of Highly Functionalized Pyridin‐4‐ones

A general protocol for the efficient synthesis of a variety of highly functionalized pyridin‐4‐ones has been developed through a sequential Wolff rearrangement and [3+3] annulation reaction of enaminones and diazo compounds. This straightforward approach features wide substrate applicability, good substrate tolerance, moderate to excellent yields, and without any catalyst, and enables access to structurally diverse pyridin‐4‐one skeletons. Additionally, scale‐up experiments and synthetic derivatizations demonstrated the potential synthetic utility of the transformations.