Enantioselective C-P cross-coupling of diarylphosphines and ortho-substituted aryl iodides has been achieved with >90%ee, using an in situ catalyst prepared from Et,Et-FerroTANE, Pd(2)(dba)(3) x CHCl(3) and LiBr.

Asymmetric catalytic hydrogenation of 2‐(2‐methoxy‐2‐oxoethyl)acrylic acid (5) to give (2S)‐4‐methoxy‐2‐methyl‐4‐oxobutanoic acid [(S)‐6] was studied. An enantiomeric excess of 99.7% ee was achieved with a catalyst formed in situ from [Rh(COD)2]BF4 and the chiral phosphite L2 in 1,2‐dichloroethane as solvent. In addition, enzyme‐catalyzed semi‐saponification of dimethyl 2‐methylsuccinate was investigated. Mono ester (S)‐6 was transformed into a few compounds which can serve as C5‐building blocks in natural product syntheses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Organo-phosphorus compoundsOrgano-phosphorus compounds S 0080 Preparation of Chiral Triarylphosphines by Pd-Catalyzed Asymmetric P-C Cross-Coupling. -Enantioselective C-P cross-coupling of diarylphosphines (II) and ortho-substituted aryl iodides (I) is achieved with high enantioselectivity using a catalyst system prepared in situ from Et,Et-FerroTANE, Pd2 (dba)3 and LiBr. -(KORFF, C.; HELMCHEN*, G.; Chem. Commun. (Cambridge) 2004, 5, 530-531; Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, Germany; Eng.) -M. Paetzel 28-179