[structure: see text] A new series of ligands with a novel phosphine-aminophosphine ligation design as depicted in structure 1 has been prepared on a ferrocenylethyl backbone. These BoPhoz ligands of structure 2 have afforded exceedingly high activity and enantioselectivity in the rhodium-catalyzed asymmetric hydrogenation of dehydro-alpha-amino acid derivatives, itaconic acids, and alpha-ketoesters. These air-stable ligands are readily prepared from cost-effective and non-pyrophoric intermediates.

A new class of bidentate ligands utilizing a phosphine-aminophosphine structure has been prepared on a ferrocenylethyl backbone in a straightforward and scalable fashion from acetylferrocene. The unique property of the alpha-ferrocenyl carbonium ion that allows the replacement of a variety of "leaving groups" with retention of configuration greatly facilitates the synthesis, and a number of ligands have been prepared by varying the nitrogen and phosphorus substituents on the aminophosphine. These readily prepared phosphinoferrocenylaminophosphines, known as BoPhoz ligands, show surprising hydrolytic and air stability, with no degradation after 3 years open to the air. The rhodium complexes of these ligands show exceedingly high enantioselectivities (generally >95% ee) and activities often in excess of 50,000 catalyst turnovers per hour for the asymmetric hydrogenation of a wide variety of dehydro-alpha-amino acid and itaconic acid derivatives. They also show high activity and good to excellent enantioselectivity for the hydrogenation of a number of alpha-ketoesters.

Enantioselective syntheses O 0031Synthesis and Application of Phosphinoferrocenylaminophosphine Ligands for Asymmetric Catalysis. -The Rh-complexes of the new ligands (I) are found to be excellent catalysts for the asymmetric hydrogenation of a wide range of dehydroamino acid derivatives, itaconates, and α-ketoesters. The ligands display high hydrolytic and air stability. -(BOAZ*, N. W.; MACKENZIE, E. B.; DEBENHAM, S. D.; LARGE, S. E.; PONASIK, J. A.

2002 reduction, hydrogenation reduction, hydrogenation O 0220 -050Phosphinoferrocenylaminophosphines as Novel and Practical Ligands for Asymmetric Catalysis.-The title phosphines are found to be efficient ligands for the asymmetric hydrogenation of dehydro-α-amino acids, itaconic acids, and α-ketoesters. -(BOAZ, NEIL W.; DEBENHAM, SHERYL D.; MACKENZIE, ELAINE B.; LARGE, SHANNON E.;