Synthesis and application of phosphinoferrocenylaminophosphine ligands for asymmetric catalysis.
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.
Boaz
Neil W
NW
Research Laboratories, Eastman Chemical Company, P.O. Box 1972, Kingsport, Tennessee 37662, USA. nwboaz@eastman.com
Mackenzie
Elaine B
EB
Debenham
Sheryl D
SD
Large
Shannon E
SE
Ponasik
James A
JA
D000596:Amino Acids / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D004952:Esters / Q000138:chemical synthesis / Q000737:chemistry; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry; D006865:Hydrogenation; D008024:Ligands; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010720:Phosphines / Q000138:chemical synthesis / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
D000596:Amino Acids; D004952:Esters; D005296:Ferrous Compounds; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D012238:Rhodium