Complexes composed of either Pd or Ru as central metal and ligands with axial chirality in all cases were used as hydrogenation catalysts. The ligands were (R)- and (S)-6,6'-dimethyl-2,2'-diaminobiphenyl, (R)-(+)-1-1'-Bi(2-naphtylamine), (R)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene and (R)-2,2'-Bis(di-p-tolylphosphino)-1,1'-binaphthyl. The Pd(II) complexes had one diamine ligand and the Ru(II) complexes had one bisphosphine and one diamine ligand, forming seven member chelate rings with the metal center. The pro-chiral substrates used were itaconic acid, alpha-acetamidocinnamic acid and acetophenone. The Pd complexes showed 100% chemoselectivity toward the C=C bond, and toward the C=O bond in the case of Ru. The yield and enantiomeric excess versus time behavior was studied using a large substrate/catalyst ratio. The addition of an organic base to the reaction with Pd complexes enhanced yield and enantiomeric excess. Use of the (S)-diamine ligand in the complex favored the (R)-products. The best results with itaconic acid were 61% yield and 56% enantiomeric excess and 55% yield and 52% enantiomeric excess with alpha-acetamidocinnamic acid, both catalyzed by Pd(OCOCF3)(2) ((S)-6,6 '-dimethyl-2,2 '-diaminobiphenyl) in 2,2,2-trifluoroethanol. In the case of the Ru catalysts, (S)-1-phenylethanol formed preferentially during hydrogenation of acetophenone. Potassium tert-butoxide stabilized the enantiomeric excess. The best result was 87% yield and 41% enantiomeric excess catalyzed by ((R)-2,2 '-Bis(di-p-tolylphosphino)-1,1 '-binaphthyl)-RuCl2-((R)-(+)-1-1 '-Bi(2-naphtylamine)). (C) 2013 Elsevier B. V. All rights reserved.