Catalytic Cycloalumination for the Synthesis of Norbornane-Annulated Phospholanes

An effective one-pot method for the synthesis of polycyclic phospholanes by in situ reaction of dichlorophosphines (RPCl2, where R = Ph, t-Bu, Me) with norbornane-annulated aluminacyclopentanes was obtained by catalytic cycloalumination of norbornenes. Oxidation of phospholanes gave the corresponding polycyclic phospholane 3-oxides (3-sulfides). The molybdenum complex L2Mo(CO)4 (L = 3-phenyl-3-phosphatricyclo[5.2.1.02,6]decane) was prepared for the first time by the reaction of 3-phenyl-3-phosphatricyclo[5.2.1.02,6]decane with molybdenum hexacarbonyl. The structures of the obtained compounds were confirmed by X-ray diffraction and multinuclear 1H, 13C, and 31P NMR spectroscopy.