80160-35-6Relevant articles and documents
Resolutions involving metal complexation. Preparation and resolution of (R,S)-methylphenyl(8-quinolyl)phosphine and its arsenic analogue. Crystal and molecular structure of (+)589-[(R)-dimethyl(1-ethyl-α-naphthyl)aminato-C 2,N]-[(S)-methylphenyl(8-quinolyl)phosphine]palladium(II) hexafluorophosphate
Allen, David G.,Mclaughlin, George M.,Robertson, Glen B.,Steffen, William L.,Salem, Geoffrey,Wild, Stanley Bruce
, p. 1007 - 1014 (2008/10/08)
The asymmetric bidentates (R,S)-methylphenyl(8-quinolyl)phosphine and (R,S)-methylphenyl(8-quinolyl)arsine have been prepared in high yield from 8-chloroquinoline and the respective substituted phosphide or arsenide anion in tetrahydrofuran at -78°C. Both compounds are air-stable crystalline solids. An efficient and large-scale resolution of both substances is described, which is based upon the fractional crystallization of a pair of internally diastereoisomeric palladium(II) complexes containing the chiral chelating ligand and an optically active ortho-metalated dimethyl(1-ethyl-α-naphthyl)amine. The optically pure enantiomers of the tertiary phosphine have [α]D±107° (mp98°C) and the corresponding arsine [α]D±115° (mp 75-76°C) in diethyl ether solution. The molecular structure and absolute configuration of (+)589-[(R)-dimethyl-(1-ethyl-α-naphthyl)aminato-C 2,N][(S)-methylphenyl(8-quinolyl)phosphine]palladium(II) hexafluorophosphate has been determined by a single-crystal X-ray analysis. The complex crystallizes in space group P212121 with a = 25.784 (5) A?, b = 19.159 (3) A?, c = 12.277 (2) A?, and Z = 8. The structure was solved by heavy-atom methods and refined by least-squares methods to an R of 0.079 and Rw of 0.047 for 2955 reflections. The tertiary phosphine liberated from this complex, [α]D -107° (diethyl ether), accordingly has the R absolute configuration.
