Ring Opening of 1,5-Dioxaspiro[3.2]hexanes: Selective Preparation of α-Heterofunctionalized-β‘-hydroxy Ketones or 2,2-Disubstituted Oxetanes

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.