title: Stereochemical specificity of the biosynthesis of the alkyl ether bond in alkyl ether lipids.
abstract: The stereochemical course of the formation of the alkyl ether bond in alkyl ether lipids was investigated through the synthesis of stereospecifically labeled acyl R- or S-[1-3H]dihydroxyacetone 3-phosphate (DHAP) starting from L-glyceraldehyde. It was demonstrated directly that the formation of the alkyl ether bond results in the stereospecific exchange of the pro-R C-1 hydrogen of DHAP with a proton of water. The configuration of the hydrogen that is retained on C-1 after formation of the alkyl ether bond was also investigated. The alkyl ether lipid was degraded, and the DHAP backbone isolated as glycerol, converted to DHAP via glycerol 3-phosphate and treated with either aldolase or triose phosphate isomerase. The results demonstrated that the retained hydrogen on C-1, which was pro-S in the starting substrate, was pro-S in the product alkyl ether.
mesh_terms: D002250:Carbon Radioisotopes; D055598:Chemical Phenomena; D002621:Chemistry; D004099:Dihydroxyacetone Phosphate; D004987:Ethers; D005634:Fructose-Bisphosphate Aldolase; D005985:Glyceraldehyde; D005993:Glycerolphosphate Dehydrogenase; D007553:Isotope Labeling; D007770:L-Lactate Dehydrogenase; D008055:Lipids; D008968:Molecular Conformation; D014305:Triose-Phosphate Isomerase; D014306:Trioses; D014316:Tritium
chemical_list: D002250:Carbon Radioisotopes; D004987:Ethers; D008055:Lipids; D014306:Trioses; D014316:Tritium; D005985:Glyceraldehyde; D004099:Dihydroxyacetone Phosphate; D005993:Glycerolphosphate Dehydrogenase; D007770:L-Lactate Dehydrogenase; D005634:Fructose-Bisphosphate Aldolase; D014305:Triose-Phosphate Isomerase