Rhodium‐BisbenzodioxanPhos Complex‐Catalyzed Homogeneous Enantioselective Pauson–Khand‐Type Cyclization in Alcoholic Solvents

The chiral atropisomeric diphosphane ligand (S)‐BisbenzodioxanPhos was found to be highly effective in the co‐operative processeses of aldehyde decarbonylation and cascaded enantioselective Pauson–Khand‐type reactions. Various 1,6‐enynes were transformed to the corresponding bicyclic cyclopentenones in good yields and enantiomeric excesses (up to 96% ee). The attractive feature of this new Rh‐catalyzed homogeneous dual catalysis system is that the reaction can be performed in alcoholic solution.