Asymmetric <i>syn</i>-dihydroxylation
and dioxyacylation of alkenes have been well established. A direct method for
the enantioselective preparation of orthogonally protected <i>syn</i>-1,2-diols from alkenes is unprecedented. Here in, we report the
first enantioselective hypervalent iodine catalyzed<i> syn</i>-hydroxy-oxyacylation of enones. The orthogonally protected diols
were obtained with excellent diastereo- and regioselectivity under metal-free
condition. For these electron-deficient alkenes, even the <i>syn</i>-dihydroxylation and dioxyacylation have remained yet an
unfinished challenge.