Chiral 1,4-diphosphines, 1,4-diphosphites and 1,4-diphosphonites from optically active (Z)-olefins as ligands for metal-catalyzed asymmetric hydrogenation and hydroformylation reactions

Chiral bidentate diphosphines and diphosphonites (1R,4R,2Z)- and (1S,4S,2Z)-RCH(PY2)CH:CHCH(PY2)R1, diphosphites and diphosphinites (1R,4R,2Z)- and (1S,4S,2Z)-RCH(OPY2)CH:CHCH(OPY2)R1 [R, R1 = (hetero)aryl, C1-10 alkyl, carboxy; Y = (hetero)aryl, aryloxy, C3-10 (cyclo)alkyl, alkoxy] useful as ligands for transition metal-catalyzed asym. hydrogenation, hydroformylation and hydrocyanation reactions, were prepd. by phosphination of the corresponding butenediols (1S,4S,2Z)- and (1S,4S,2Z)-RCH(OH)CH:CHCH(OH)R1 by optionally axial-chiral phosphorus reagents LiPY2 or ClPY2. Ruthenium, rhodium and palladium complexes were prepd. or generated in situ by ligand substitution of [Ru(p-cymene)I2]2, [Rh(NBD)]BPh4, [Rh(COD)2]ClO4 and [Pd(PhCN)2Cl2], resp. and tested as catalysts in asym. hydrogenation of Et 2-(benzamidomethyl)-3-oxobutanoate and hydroformylation of (3S,4R)-3-[(R)-1-(tert-butyldimethylsiloxy)ethyl]-4-vinylazetidin-2-one.