Divergent Chemo-, Regio-, and Diastereoselective Normal Electron-Demand Povarov-Type Reactions with α-Oxo-ketene Dienophiles

The reactions between electron-rich 2-azadienes and alpha-oxo-ketenes derived from the Wolff rearrangement of 2-diazocycloalkane-1,3-diones chemo- and regioselectively produced spiro hydropyrid-4-ones with good to excellent diastereoselectivities. These reactions are likely to proceed via a domino Wolff/Friedel-Crafts/intramolecular Mannich process. Prolonged domino sequences also allowed the expeditious preparation of a series of pyrazolopyridine and pyridopyrimidine heterocycles.