Asymmetric hydrogenation with chiral aminophosphine-rhodium complexes and chiral recognition by bisphosphine-rhodium complexes in the asymmetric hydrogenation of olefins through the chiral helical conformation of phenyl groups on the phosphorus atom.
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The asymmetric hydrogenation of α-acylaminocinnamic acids with the rhodium complex of (1<I>R</I>,2<I>R</I>)-1,2-bis(<I>N</I>-diphenylphosphino-<I>N</I>-methylamino)cyclohexane has been reported to give preferentially (<I>S</I>)-amino acids. On the contrary, it has been found that the enantiomeric (<I>R</I>)-amino acids are obtained by hydrogenation with the rhodium complex of (1<I>R</I>,2<I>R</I>)-1,2-bis(diphenylphosphinamino)cyclohexane. The study of the inversion of the stereoselectivity of the rhodium complex of (1<I>R</I>,2<I>R</I>)-1,2-bis(diphenylphosphinamino)cyclohexane by the <I>N</I>-methylation of the ligand in asymmetric hydrogenation has been described. From stereochemical considerations, the chiral helical conformation of the phenyl groups attached on the phosphorus in bisphosphine-rhodium complexes may be responsible for the induced chirality of the product of the hydrogenation. A complex with a left-handed helicity would give (<I>R</I>)-amino acid, and a complex with a right-handed helicity would give (<I>S</I>)-amino acid. The effects of the solvents and substrate structures on the optical yields are also discussed.
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関連論文
- The crystal and molecular structure of (trans-1,2-bis(diphenylphosphinamino)cyclohexane)(1,5-cyclooctadiene)rhodium(I) perchlorate dichloromethane solvate.
- The asymmetric homogeneous hydrogenation of olefins with the rhodium complexes of (1S,2S)-1,2bis(diphenylphosphinamino)cyclohexane and (2S,3S)-2,3-bis(diphenylphosphinamino)butane.
- Asymmetric hydrogenation with chiral aminophosphine-rhodium complexes and chiral recognition by bisphosphine-rhodium complexes in the asymmetric hydrogenation of olefins through the chiral helical conformation of phenyl groups on the phosphorus atom.