Mild and simple catalytic systems consisting of molybdenum(VI) dichloride dioxide MoO2Cl2] as a catalyst and a phosphine as reductant have been developed for the stereospecific deoxygenation of epoxides to alkenes. The reactions using 1,2‐bis(diphenylphosphino)ethane (dppe) and triphenylphosphine (PPh3) proceed with retention and inversion of stereochemistry, respectively. The mild reaction tolerates the presence of various functional groups and affords stereodefined substituted olefins in good yields.
