Aminophosphonite-phosphite and aminophosphonite-phosphinite chiral ligands with mixed stereogenic elements have been prepared in good yields from chiral alpha-aminoalcohols such as 2-(hydroxymethyl)pyrrolidine and 2-N-ethylammino-1-butanol. These new ligands have been fully characterized; the Rh(l) complexes have been tested in catalytic hydrogenation and hydroformylation reactions. Enantioselectivities up to 70% have been obtained in asymmetric hydrogenation of alpha-acetamidocinnamic acid, methyl ester; enantioselectivities higher than 30% and regioselectivities higher than 98% have been obtained in asymmetric hydroformylation of vinyl acetate. (C) 2003 Elsevier Science B.V. All rights reserved.