Optically active transition-metal complexes. 10. Bifunctional arene-chromium-tricarbonyl complexes derived from (R)-phenylethanamine: Easily accessible planar-chiral diphosphines and their application in enantioselective hydrogenation, hydroamination, and allylic sulfonation

(R)-[{alpha-(Dimethylamino)ethyl}-eta(6)-benzene]Cr(CO)(3) is stereoselecti vely substituted in the ortho-position with PPh2, P(O)Ph-2, and CO2R groups . After exchange of the amino group for a chloro substituent with chlorofor mic eaters, a variety of phosphorus, nitrogen, and oxygen nucleophiles can be diastereoselectively introduced into the alpha-position to generate bifu nctional chelating ligands. The addition of cyanide is not fully diastereos pecific. The diphosphines, structurally similar to the well-known "Josiphos "-ferrocenes, are good catalysts for rhodium-catalyzed enantioselective hyd rogenation, iridium-catalyzed hydroamination, and palladium-catalyzed allyl ic sulfonation.