Chiral biphenyl diphosphines for asymmetric catalysis: stereoelectronic design and industrial perspectives.
Two original chiral diphosphines, SYNPHOS and DIFLUORPHOS, have been synthesized on multigram scales. Their steric and electronic profiles have been established in comparison with the commonly used 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and 6,6'-dimethoxy-2,2'-bis(diphenylphosphino)-1,1'-biphenyl ligands. A screening study of the four ligands in Ru(II)-catalyzed asymmetric hydrogenation of prochiral ketones and olefins has been performed. It revealed that the stereoelectronic features of the ligand and the substrate deeply influenced the enantioselectivities obtained in asymmetric hydrogenation, SYNPHOS and DIFLUORPHOS being fully complementary in terms of enantioselectivity for this reaction.
Jeulin
Séverine
S
Laboratoire de Synthèse Sélective Organique et Produits Naturels, Ecole Nationale Supérieure de Chimie de Paris, 11 Rue Pierre et Marie Curie, 75231 Paris Cedex 05, France.
de Paule
Sébastien Duprat
SD
Ratovelomanana-Vidal
Virginie
V
Genêt
Jean-Pierre
JP
Champion
Nicolas
N
Dellis
Philippe
P