Synthesis of optically active phosphiranes and their use as ligands in rhodium(I) complexes

Article abstract of DOI:10.1021/om00028a040

Optically active (phosphirane) Mo(CO)₅ complexes have been obtained by starting from chiral styrene oxide. The corresponding tervalent phosphiranes are easily recovered through a stereoselective decomplexation reaction and used as ligands for cationic rhodium complexes. Some preliminary results on the catalytic hydrogenation of olefins show that different diastereoisomers of a phosphirane give a completely different catalytic behavior to their rhodium complexes. Unusually for a monodentate phosphine, significant optical yields are obtained with one of the four diastereoisomers of the P-menthylphosphirane. The actual involvement of phosphirane itself in the catalytic cycle is not fully established.