A nickel­(II)-catalyzed oxygen transfer reaction of dibenzylideneacetone-derived N-vinyl-α,β-unsaturated nitrones has been identified for the preparation of polysubstituted 2-(pyridin-2-yl)­ethanols in good yields with high atom economy. The scope of the method is described, and mechanistic experiments are discussed. The reaction was easily performed at gram scales, and pyrido­[2,3-c]­carbazole was obtained in moderate yield over three steps.

We describe a DBU‐controlled 6π‐azaelectrocyclization of dibenzylideneacetone‐derived N‐vinyl‐α,β‐unsaturated nitrones to prepare 6‐alkyl pyridine N‐oxides in 24–82% yields. Mechanistic studies revealed that DBU had a great impact on the formation of 6‐alkyl pyridine N‐oxides and served as a base and the carrier of hydrogen sources to in situ reduce C=C bonds. The 6‐alkyl pyridine N‐oxide was prepared at gram‐scales and converted to estrone‐derived pyridine and pyrido[2,3‐c]carbazole 4‐oxide in 46% and 52% yields in two steps, respectively.