Regio- and Stereoselective Addition of HO/OOH to Allylic Alcohols.

A range of allylic alcohols are shown to readily react with ethereal HO in the presence of catalytic amounts of NaMoO-gly or MoO(acac), affording the C═C trans hydroxylation-hydroperoxylation products in good yields with high regio- and stereoselectivity. Use of enantiomers of cyclic substrates resulted in corresponding enantiopure diol--hydroperoxides. The possibility of further conversion of the diol--hydroperoxides into triols or linear building blocks with an isolated -peroxy group containing a quaternary center is also exemplified.