ENANTIOSELECTIVE CATALYSIS .53. ENANTIOSELECTIVE CATALYSIS WITH RH COMPLEXES CONTAINING OPTICALLY-ACTIVE IRON COMPOUNDS AS LIGANDS - CRYSTAL-STRUCTURE OF CPFE(CO)(COME)PPH2ORH(COD)

Cleavage of the PN bond in (+)436- and (-)436-CpFe(CO)(COMe)PPh2NMeCHMePh with aqueous HBF4 gives (+)436- and (-)436-CpFe(CO)(COMe)PPh2OH. The reactions of (+)436- and (-)436-CpFe(CO)(COMe)PPh2OH with [Rh(COD)Cl]2/KOH give the binuclear complexes (+)436- and (-)436-CpFe(CO)(COMe)PPh2ORh(COD). These complexes and the in situ catalysts, consisting of the procatalyst [Rh(COD)Cl]2 and the cocatalysts (+)- and (-)-CpFe(CO)(COMe)-Diop, were used in the enantioselective hydrogenation of Z-α-N-acetamidocinnamic acid and in the enantioselective hydrosilylation of acetophenone with diphenylsilane. Optical inductions of up to 76% were obtained in the hydrogenation and 6.1% in the hydrosilylation reaction. The structure of CpFe(CO)(COMe)PPh2ORh(COD) was determined by X-ray diffraction. © 1990.