THE RESOLUTION OF RACEMIC HYDROPEROXIDES - A CHROMATOGRAPHY-BASED SEPARATION OF PERKETALS DERIVED FROM ARACHIDONIC, LINOLEIC, AND OLEIC-ACID HYDROPEROXIDES

被引:21
作者
PORTER, NA
DUSSAULT, P
BREYER, RA
KAPLAN, J
MORELLI, J
机构
[1] Department of Chemistry, Duke University, Durham
[2] Department of Chemistry, University of Nebraska, Lincoln
关键词
D O I
10.1021/tx00015a008
中图分类号
R914 [药物化学];
学科分类号
100701 ;
摘要
In spite of the importance of optically pure unsaturated hydroperoxides in biology, chemistry, and medicine, no general method for synthesizing these labile compounds has been reported. We have developed a chiral vinyl ether that reacts with racemic hydroperoxides to give diastereomeric perketals in high yield. These perketals can be separated by liquid chromatography and the chiral group removed to provide highly enriched hydroperoxide enantiomers (>99% enantiomeric excess). The chiral reagent that has been most successful in our hands is the 2-propenyl ether derived from írans-2-phenylcyclohexanol. By use of this vinyl ether, perketals are readily formed from hydroperoxides, they are stable to normal- and reverse-phase chromatography, and the hydroperoxide is regenerated from the perketal without racemization in high yield with mild acid. Several chiral hydroperoxides have been resolved by this procedure: -phenethyl hydroperoxide, 2-octyl hydroperoxide, and a number of hydroperoxides derived from oleic, linoleic, and arachidonic acids. © 1990, American Chemical Society. All rights reserved.
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页码:236 / 243
页数:8
相关论文
共 35 条
[1]   ENANTIOSPECIFIC AND STEREOSPECIFIC SYNTHESIS OF LIPOXIN-A - STEREOCHEMICAL ASSIGNMENT OF THE NATURAL LIPOXIN-A AND ITS POSSIBLE BIOSYNTHESIS [J].
ADAMS, J ;
FITZSIMMONS, BJ ;
GIRARD, Y ;
LEBLANC, Y ;
EVANS, JF ;
ROKACH, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (02) :464-469
[2]  
ALEXAKIS A, 1977, B SOC CHIM FR II-CH, P693
[3]   DETERMINATION OF STEREOCHEMISTRY IN THE FATTY-ACID HYDROPEROXIDE PRODUCTS OF LIPOXYGENASE CATALYSIS [J].
ANDRE, JC ;
FUNK, MO .
ANALYTICAL BIOCHEMISTRY, 1986, 158 (02) :316-321
[4]   ABSOLUTE-CONFIGURATION OF CIS-12-OXOPHYTODIENOIC ACID OF FLAXSEED - IMPLICATIONS FOR THE MECHANISM OF BIOSYNTHESIS FROM THE 13(S)-HYDROPEROXIDE OF LINOLENIC ACID [J].
BAERTSCHI, SW ;
INGRAM, CD ;
HARRIS, TM ;
BRASH, AR .
BIOCHEMISTRY, 1988, 27 (01) :18-24
[5]   CONVENIENT AND GENERAL PREPARATION OF ALKYL HYDROPEROXIDES AND DIALKYL PEROXIDES [J].
COOKSON, PG ;
DAVIES, AG ;
ROBERTS, BP .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1976, (24) :1022-1023
[6]   CONTROLLED CHEMICAL SYNTHESIS OF THE ENZYMATICALLY PRODUCED EICOSANOIDS 11-HETE, 12-HETE, AND 15-HETE FROM ARACHIDONIC-ACID AND CONVERSION INTO THE CORRESPONDING HYDROPEROXIDES (HPETE) [J].
COREY, EJ ;
MARFAT, A ;
FALCK, JR ;
ALBRIGHT, JO .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (04) :1433-1435
[7]   THE RESOLUTION OF RACEMIC HYDROPEROXIDES - THE PREPARATION OF OPTICALLY PURE HYDROPEROXIDE NATURAL-PRODUCTS [J].
DUSSAULT, P ;
PORTER, NA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (18) :6276-6277
[8]   PREPARATION AND PURIFICATION OF LIPID HYDROPEROXIDES FROM ARACHIDONIC AND GAMMA-LINOLENIC ACIDS [J].
FUNK, MO ;
ISAAC, R ;
PORTER, NA .
LIPIDS, 1976, 11 (02) :113-117
[9]   OXYGENATION OF TRANS POLYUNSATURATED FATTY-ACIDS BY LIPOXYGENASE REVEALS STERIC FEATURES OF THE CATALYTIC MECHANISM [J].
FUNK, MO ;
ANDRE, JC ;
OTSUKI, T .
BIOCHEMISTRY, 1987, 26 (21) :6880-6884
[10]  
GALLIARD T, 1980, LIPOXYGENASES, P131