天竺葵属植物中氧化橙花醇的结构解析、对映体选择性分析及生物合成

Structure elucidation, enantioselective analysis, and biogenesis of nerol oxide in Pelargonium species.

作者信息

Wüst M, Reindl J, Fuchs S, Beck T, Mosandl A

机构信息

Institut für Lebensmittelchemie, Biozentrum, Johann Wolfgang Goethe-Universität, Frankfurt, Germany.

出版信息

J Agric Food Chem. 1999 Aug;47(8):3145-50. doi: 10.1021/jf981245m.

DOI:10.1021/jf981245m

PMID:10552622

Abstract

A novel enantioselective synthesis of nerol oxide (3, 6-dihydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran) was used for the determination of the absolute configuration at C-2. The order of elution of the enantiomers on octakis-(2, 3-di-O-butyryl-6-O-tert-butyldimethylsilyl)-gamma-cyclodextrin in OV 1701-vi as the chiral stationary phase in enantioselective GC was determined as (2R) before (2S). Enantioselective multidimensional GC/MS (enantio-MDGC/MS) was used for the determination of the enantiomeric ratios of nerol oxide in different geranium oils. As a result, in all investigated oils nerol oxide occurs as a racemate. The biogenesis of nerol oxide in Pelargonium species was investigated by feeding experiments using deuterium-labeled neryl glucoside as the precursor. The Pelargonium plants were able to convert the fed precursor into racemic nerol oxide, which has to be considered as a "natural racemate".

摘要

一种用于确定C-2位绝对构型的橙花叔醇氧化物（3,6-二氢-4-甲基-2-(2-甲基-1-丙烯基)-2H-吡喃）的新型对映选择性合成方法被采用。在对映选择性气相色谱中，以八-(2,3-二-O-丁酰基-6-O-叔丁基二甲基甲硅烷基)-γ-环糊精为手性固定相、OV 1701-vi为载体时，对映体的洗脱顺序被确定为(2R)先于(2S)。对映选择性多维气相色谱/质谱联用（对映体多维气相色谱/质谱联用，enantio-MDGC/MS）被用于测定不同天竺葵油中橙花叔醇氧化物的对映体比例。结果显示，在所有研究的油中，橙花叔醇氧化物均以外消旋体形式存在。通过使用氘标记的橙花醇葡萄糖苷作为前体进行饲喂实验，研究了天竺葵属植物中橙花叔醇氧化物的生物合成。天竺葵属植物能够将饲喂的前体转化为外消旋的橙花叔醇氧化物，这必须被视为一种“天然外消旋体”。