TY - JOUR
T1 - The resolution of racemic hydroperoxides
T2 - A chromatography-based separation of perketals derived from arachidonic, linoleic, and oleic acid hydroperoxides
AU - Porter, Ned A.
AU - Dussault, Patrick
AU - Breyer, Robert A.
AU - Kaplan, Jere
AU - Morelli, Joseph
PY - 1990
Y1 - 1990
N2 - 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.
AB - 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.
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U2 - 10.1021/tx00015a008
DO - 10.1021/tx00015a008
M3 - Article
C2 - 2131835
AN - SCOPUS:0025188649
SN - 0893-228X
VL - 3
SP - 236
EP - 243
JO - Chemical Research in Toxicology
JF - Chemical Research in Toxicology
IS - 3
ER -