Catalytic-Enantioselective Methoxycarbonylation of 1,3-Dichloroarenetricarbonyl-chromium(0) Complexes: A Desymmetrization Approach to Planar Chirality

Abstract The Pd-catalyzed mono-methoxycarbonylation of pro­chiral 1,3-dichloroarene-Cr(CO) 3 complexes was investigated. In the presence of the chiral ferrocene ligand (R,S P )-PPF-pyrrolidine the planar-chiral products were obtained with up to 90% ee (53% yield). A strong dependence of the enantioselectivity on the reaction time was observed. A kinetic study using η 6 -(2,6-dichlorotoluene)-Cr(CO) 3 revealed that the initial enantiomeric purity of the mono-methoxycarbonylated product is further enhanced due to a kinetic resolution (S = 4.3) connected to the formation of the bis-methoxycarbonylated side-product.