Stereochemical studies of chiral resolving agents, M9PP and H9PP acids.
The stereoselective Grignard reaction of (1R,2S,5R)-(-)-2-isopropyl-5-methylcyclohexyl pyruvate (menthyl pyruvate) with 9-phenanthrylmagnesium bromide yielded diastereomeric hydroxy-esters, where intramolecular OH em leader O=C hydrogen bond was observed in IR and (1)H NMR spectra. The alkaline hydrolysis of the major product gave (+)-2-hydroxy-2-(9-phenanthryl)propionic acid (H9PP acid (3)), whose absolute configuration was assigned as S based on the chemical correlation with (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl ester of (S)-2-methoxy-2-(9-phenanthryl)propionic acid (M9PP acid (2)); the absolute configuration of 2 had been previously established by X-ray crystallography. The enantioresolution of (+/-)-6-methyl-5-hepten-2-ol, sulcatol, an insect pheromone, was carried out using (S)-(+)-M9PP acid 2.
National Institute of Agrobiological Sciences, Tsukuba, Ibaraki, Japan. ichikawa@affrc.go.jp
Akio
A
Ichikawa
Hiroshi
H
Ono
Nobuyuki
N
Harada
D002851:Chromatography, High Pressure Liquid; D004952:Esters / Q000737:chemistry*; D006880:Hydroxy Acids; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010616:Phenanthrenes / Q000138:chemical synthesis / Q000737:chemistry*; D011422:Propionates / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
C492686:2-hydroxy-2-(9-phenanthryl)propionic acid; C492685:2-methoxy-2-(9-phenanthryl)propionic acid; D004952:Esters; D006880:Hydroxy Acids; D010616:Phenanthrenes; D011422:Propionates; C029658:propionic acid