甘油部分的立体特异性标记：1,2-二油酰基-sn-[3-³H]甘油-3-磷酸（1-外消旋甘油）的合成

Stereospecific labeling of the glycerol moiety: synthesis of 1,2-dioleoyl-sn-[3-3H]glycero-3-phospho(1-rac-glycerol).

作者信息

Schmitt J D, Amidon B, Wykle R L, Waite M

机构信息

Department of Biochemistry, Wake Forest University Medical Center, Winston-Salem, NC 27157-1016, USA.

出版信息

Chem Phys Lipids. 1995 Aug 25;77(2):131-7. doi: 10.1016/0009-3084(95)02461-q.

DOI:10.1016/0009-3084(95)02461-q

PMID:7586097

Abstract

1,2-Dioleoyl-sn-[3-3H]glycero-3-phospho(1-rac-glycerol) was synthesized from 1,2-dioleoyl-sn-glycerol using a new radiosynthetic procedure. 1,2-Dioleoyl-sn-glycerol was oxidized to the corresponding aldehyde using pyridinium dichromate and pyridine. The aldehyde was reduced to the radiolabeled alcohol using tritiated sodium borohydride and crown ether. This material was then converted to the phosphocholine derivative using 2-chloro-2-oxo-1,3,2-dioxaphospholane, followed by displacement with trimethylamine. In the last step, the 1,2-dioleoyl-sn-[3-3H]glycero-3-phosphocholine was converted to 1,2-dioleoyl-sn-[3-3H]glycero-3-phospho-(1-rac-glycerol) via a classic transphosphatidylation reaction using glycerol and cabbage phospholipase D. A theoretical explanation of unusual chemical behavior of the primary alcohol of diglycerides is also given, based on semi-empirical calculations.

摘要

采用一种新的放射性合成方法，由1,2 - 二油酰 - sn - 甘油合成了1,2 - 二油酰 - sn - [3 - ³H]甘油 - 3 - 磷酸（1 - 外消旋甘油）。使用重铬酸吡啶鎓和吡啶将1,2 - 二油酰 - sn - 甘油氧化为相应的醛。使用氚化硼氢化钠和冠醚将醛还原为放射性标记的醇。然后使用2 - 氯 - 2 - 氧代 - 1,3,2 - 二氧磷杂环戊烷将该物质转化为磷酸胆碱衍生物，随后用三甲胺进行取代。在最后一步中，通过使用甘油和甘蓝磷脂酶D的经典转磷脂酰化反应，将1,2 - 二油酰 - sn - [3 - ³H]甘油 - 3 - 磷酸胆碱转化为1,2 - 二油酰 - sn - [3 - ³H]甘油 - 3 - 磷酸 - （1 - 外消旋甘油）。基于半经验计算，还给出了甘油二酯伯醇异常化学行为的理论解释。