The intramolecular hydrodimerization reaction is a way to form a sigma bond between two formally electrophyilic carbon centers and it is a powerful version of the dimerization of a-b unsaturated ketones, esters and nitriles. In this reaction one new ring and up-to four stereocenters are formed. As part of our efforts directed at expanding the scope of the intramolecular hydrodimerization reaction, alkoxy tether substituted mixed enone/enoate and dienone cyclization precursors were examined. Interestingly, either elimination product 1 or retention product 2 could be prepared by hydrodimerization under electrochemical conditions, with the product type being determined by the protecting group on oxygen. The retention product 2 was formed as a single isomer, indicating that this single stereocenter is capable of controlling the facial selectivity of the reaction. Efforts are underway to extend the power of the intramolecular hydrodimerization reaction to the synthesis of biologically active natural products such as cinnamolide and avarol and also to prepare optically active cyclization precursors using the asymmetric Baylis-Hillman reaction which then can provide further deformation regarding the reaction mechanism.