Davis P A, Hajra A K
J Biol Chem. 1979 Jun 10;254(11):4760-3.
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.
通过从L-甘油醛开始合成立体特异性标记的酰基R-或S-[1-³H]二羟基丙酮3-磷酸（DHAP），研究了烷基醚脂质中烷基醚键形成的立体化学过程。直接证明了烷基醚键的形成导致DHAP的前-R C-1氢与水分子的一个质子发生立体特异性交换。还研究了形成烷基醚键后保留在C-1上的氢的构型。将烷基醚脂质降解，分离出作为甘油的DHAP主链，通过3-磷酸甘油转化为DHAP，并用醛缩酶或磷酸丙糖异构酶处理。结果表明，在起始底物中为前-S的C-1上保留的氢，在产物烷基醚中也是前-S。
