New P-chirogenic diphosphines and their use in catalytic asymmetric reactions*

and (R,R)-1,1-bis(alkylmethylphosphino)methanes (alkyl = isopropyl, t-butyl, cyclohexyl, phenyl) (abbreviated as MiniPHOS) were prepared from phosphorus trichloride via short routes using phosphine–boranes as intermediates. The crystal structures of cationic rhodium complexes, [Rh((S,S)-1,2-bis((phenyl)(5',6',7',8'-tetrahydronaphthyl)phosphino)ethane)(cod)]BF4, [Rh((S,S)-t-Bu-BisP*(nbd))]BF4, and [Rh((R,R)-t-Bu-MiniPHOS)2]PF6, clearly indicate the ideal asymmetric environments. These ligands exhibited an excellent to almost perfect level of enantioselectivity in asymmetric hydrogenations of α-dehydroamino acid derivatives and other catalytic asymmetric reactions