Abstract: Enantiomerically pure substituted 1,4-dioxanes have been prepared from vinyl phenyl selenones and the commercially available enantiopure 1,2-diols in the presence of sodium hydride. This simple and novel one step procedure is an example of the Michael initiated ring closure reactions (MIRC) and involves a conjugate addition of the alkoxide anions derived from the 1,2-diols to the vinyl phenyl selenones. The carbanions thus generated then suffer a proton transfer to give the alkoxide ions which effect the intramolecular displacement of the PhSeO2 group affording the substituted 1,4-dioxanes as the result of a ring closure reaction.