Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 6. On the Selective Hydroxylation of Cubane

By using methyl(trifluoromethyl)dioxirane (TFDO), the direct mono- and bishydroxylation of cubane could be achieved in high yield under remarkably mild conditions. Comparison of the rates of dioxirane O-insertion with those of standard reference compounds, such as adamantine and cyclopropane, as well as ab initio computations provide useful hints concerning the mechanism of these transformations.