Multigram Synthesis of Mevalonolactone-d9 and Its Application to Stereochemical Analysis by 1H NMR of the Saturation Reaction in the Biosynthesis of the 2,3-Di-O-phytanyl-sn-glycerol Core of the Archaeal Membrane Lipid
Multigram Synthesis of Mevalonolactone-d9 and Its Application to Stereochemical Analysis by 1H NMR of the Saturation Reaction in the Biosynthesis of the 2,3-Di-O-phytanyl-sn-glycerol Core of the Archaeal Membrane Lipid
复制标题
甲瓦龙酸内酯-d9的多克合成及其在古菌膜脂质2,3-二-O-植烷基-sn-甘油核心生物合成中饱和反应的1H NMR立体化学分析中的应用
DOI：
10.1021/ja974387q
复制
发表时间：
1998
影响因子：
15
通讯作者：
K. Kakinuma
中科院分区：
文献类型：
--
作者：
T. Eguchi;M. Morita;K. Kakinuma
以氘代二甲氧基苯丙酮和膦酰基乙酸三甲酯为原料，开发了(RS)-甲羟戊酸内酯-d9 (8)的合成方法。在七步中，8 的总产率为 33%。合成的甲瓦龙酸内酯-d9应用于古菌核心膜脂质2,3-二-O-植烷酰-sn-甘油的生物合成研究。 Mevalonolactone-d9 高度融入古菌脂质的植烷基链中，总富集率大约高达 70%。甲羟戊酸途径显然负责古菌膜中核心脂质植烷酰链的生物合成。此外，通过 1 H NMR 光谱分析氕在重氘化古菌脂质上的行为，表明香叶基香叶基基团对植物烷基基团的饱和是通过以顺式方式加氢而发生的。
A synthetic method for (RS)-mevalonolactone-d9 (8) was developed starting from deuterated dimethoxyphenylacetone and trimethyl phosphonoacetate. The overall yield of 8 was 33% in seven steps on a multigram scale. Synthesized mevalonolactone-d9 was applied to biosynthetic studies of the archaeal core membrane lipid 2,3-di-O-phytanyl-sn-glycerol. Mevalonolactone-d9 was highly incorporated into the phytanyl chains of the archaeal lipid, and the total enrichment was approximated to be as high as 70%. The mevalonate pathway is clearly responsible for the biosynthesis of the phytanyl chains of the core lipid in the archaeal membrane. Further, saturation of the geranylgeranyl group to the phytanyl group was shown to take place through the addition of hydrogen in a syn manner by analyzing the behavior of protium on the heavily deuterated archaeal lipid by 1H NMR spectroscopy.