Friedberg S J, Gomillion D M, Stotter P L
J Biol Chem. 1980 Feb 10;255(3):1074-9.
O-Alkyl dihydroxyacetone phosphate is formed enzymatically from acyl dihydroxyacetone phosphate and a long chain fatty alcohol. This reaction is accompanied by stereospecific exchange of the pro-R hydrogen of carbon 1 (carbon 1 of all compounds corresponds to carbon 1 of sn-glycerol) of the dihydroxyacetone phosphate moiety with retention of configuration. In the present investigation, data are provided to show that the initial loss of hydrogen from carbon 1 of acyl dihydroxyacetone phosphate does not depend on the presence of the fatty alcohol. In addition, the occurrence of a Schiff base between enzyme and acyl dihydroxyacetone phosphate, comparable to the fructose-1,6-diphosphate aldolase reaction, could not be demonstrated. It is concluded that the formation of 1-O-alkyl dihydroxyacetone phosphate via the formation of intermediate 1-O-acyl endiol and 1-O-alkyl endiol is a likely mechanism.
O-烷基磷酸二羟丙酮由酰基磷酸二羟丙酮和长链脂肪醇通过酶促反应形成。此反应伴随着磷酸二羟丙酮部分的碳1（所有化合物的碳1对应于sn-甘油的碳1）的前-R氢的立体定向交换，构型保持不变。在本研究中，提供的数据表明，酰基磷酸二羟丙酮碳1上氢的初始损失不依赖于脂肪醇的存在。此外，未证实酶与酰基磷酸二羟丙酮之间存在类似于果糖-1,6-二磷酸醛缩酶反应的席夫碱。结论是，通过形成中间体1-O-酰基烯二醇和1-O-烷基烯二醇来形成1-O-烷基磷酸二羟丙酮是一种可能的机制。
