Stereochemical studies of chiral resolving agents, M9PP and H9PP acids

• Published in: Chirality (New York, N.Y.) Vol. 16; no. 8; pp. 559 - 567
• Main Authors: Ichikawa, Akio, Ono, Hiroshi, Harada, Nobuyuki
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 2004
• Subjects: (S)-(+)-H9PP acid; (S)-(+)-M9PP acid; 1H NMR anisotropy effect; absolute configuration; chiral 1H NMR anisotropy reagent; chiral resolving agent; Chromatography, High Pressure Liquid; diastereomeric esters; Esters - chemistry; HPLC separation on silica gel; Hydroxy Acids; insect pheromone; Magnetic Resonance Spectroscopy; Molecular Structure; Phenanthrenes - chemical synthesis; Phenanthrenes - chemistry; Propionates - chemical synthesis; Propionates - chemistry; Stereoisomerism; sulcatol
• ISSN: 0899-0042; 1520-636X
• DOI: 10.1002/chir.20076

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…O=C hydrogen bond was observed in IR and 1H 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. Chirality 16:559–567, 2004. © 2004 Wiley‐Liss, Inc.