Direct synthesis of 2,6-disubstituted pyridines from bicyclic ketals

6,8-Dioxabicyclo[3.2.1]octanes 1, prepared from methyl vinyl ketone dimer, have been readily converted into 2,6-disubstituted pyridine derivatives 2 in one step by treatment with AlCl3–NH2OH·HCl/AcOH. The transformation mechanism of this reaction has been studied by the preparation of a deuterium labelled 1,5-diketone, which was transformed into a pyridine via a dioxime, from the bicyclic ketal.