1154-14-9Relevant academic research and scientific papers
Synthesis of Partially Hydrogenated 2,2'-Bis(diphenylphosphenyl)-1,1'-binaphthyl (BINAP) Ligands and Their Application to Catalytic Asymmetric Hydrogenation
Zhang, Xiaoyong,Mashima, Kazushi,Koyano, Kinko,Sayo, Noboru,Kumobayashi, Hidenori,et al.
, p. 2309 - 2322 (2007/10/02)
Three pairs of new axially dissymmetric bisphosphane ligands, (R)-(-)- and (S)-(+)-2,2'-bis(dicyclohexylphosphanyl)-1,1'-binaphthyl , (R)-(+)- and (S)-(-)-2,2'-bis(diphenylphosphanyl)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl and (R)-(-)- and (S)-(+)-2,2'-bis(dicyclohexylphosphanyl)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl , have been synthesized.The absolute configurations of the isomers 2 were determined by single-crystal X-ray diffraction of the linear 1:1 polymeric complex of (S)-(+)-2,2'-bis(dicyclohexylphosphinoyl)-1,1'-binaphthyl and (2R,3R)-(-)-di-O-benzoyltartaric acid , and those of the isomers 3 and 4 were established on the basis of CD spectra of the phosphanes and their bisoxides.X-Ray crystallographic studies of two cationic RhI complexes, (cod)>ClO4 and (cod)>ClO4 , revealed that complex (S)-17 possesses a dissymmetric structure, while complex (S)-18 has a pseudo-C2-symmetry and shows a significantly large dihedral angle between the two phenyl rings .The potentiality of ligand 3 for asymmetric catalysis was demonstrated in RuII-catalysed stereoselective hydrogenations of methyl 2-(benzamidomethyl)-3-oxobutanoate (21, in up to 92percent d.e. and 99percent e.e.) and geraniol (22, in 98percent optical purity).
