2-Methyleneoxetanes have been converted into 1,5-dioxaspiro[3.2]hexanes with dimethyldioxirane. Reaction of the dioxaspirohexanes with a
range of heteroatom nucleophiles, hydride donors, or organoaluminum reagents was successful under neutral or mild conditions, affording,
selectively, polyfunctionalized ketones or 2,2-disubstituted oxetanes.