SYNTHESIS, CHIROPTICAL PROPERTIES AND ABSOLUTE CONFIGURATION OF α-PHENYLGLYCIDIC ACID

Article abstract of DOI:10.1016/S0040-4020(01)96519-6

The (+)- and (-) enantiomers of potassium α-phenylglycidate, an irreversible inhibitor of the enzyme mandelate racemase, were synthesized by resolution of the diastereomeric esters with R-(-)-2-octanol.Base-catalyzed ring-opening of the resolved α-phenylglycidate esters gave the enantiomers of 2,3-dihydroxy-2-phenylpropaonic acid, also obtained by resolution of the racemic dihydroxy acid using ephedrine.A comparison of the chiroptical properties of the esters of α-phenylglycidic and 2,3-dihydroxy-2-phenylpropionic acids with those of the structurally similar atrolactic and mandelic acids and their 2-methoxy-derivatives showed that the (-)-methyl 2,3-dihydroxy-2-phenylpropanoate corresponding to the (+)-enantiomer of potassium α-phenylglycidate, as well as the esters of α-phenylglycidic acid derived from the same (+)-potassium salt, were all configurationally related to S-(+)-atrolactic and mandelic acids.The configurational assignments made on the basis of the chiroptical data were confirmed by lithium aluminium hydride reduction of the (-)-2-octyl S- and R-α-phenylglycidates, which led exclusively to the R-(-)- and S-(+)-2-phenyl-1,2-propanediols, respectively, previously related configurationally to R-(-)- and S-(+)-atrolactic acids.