Stereochemistry of hydroxylation of some chiral spiro-[2,5]octan-4-ones

► Dioxygen oxidize some spirooctan-4-ones in DMSO (DMF)/NaOH stereoselectively. ► Hydroxylation do not change the ratio of stereoisomers obtained in cyclopropanation. ► DMSO was not oxidizing agent in alpha hydroxylation process. ► Sodium borohydride reduces some α-hydroxyketones to dioles stereoselectively. ► Three symmetry unique molecules in the crystal structure of α-hydroxyketone 2a1.