Lutnaes B F, Gautun O R, Liaaen-Jensen S
Organic Chemistry Laboratories, Faculty of Chemistry and Biology, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway.
Chirality. 2001 May 5;13(4):224-9. doi: 10.1002/chir.1023.
The question raised in the title was answered. (3R, 3'S)-meso-Zeaxanthin was submitted to iodine catalyzed photochemical stereoisomerisation. The enantiomeric (9Z) and (9'Z) geometrical isomers were isolated by semipreparative HPLC and separated as diastereomeric dicarbamates on a chiral column only. Cleavage of the carbamate could not be effected. CD-Spectra of (1"S, 1"S)- and (1"R, 1"R)-dicarbamates of geometrical isomers of (3R, 3'R)- and (3R, 3'S)-meso-zeaxanthin were systematically studied and the contribution from the carbamate moieties revealed. It was concluded that (9Z, 3R, 3'S)-"meso"-zeaxanthin, in spite of having no symmetry elements, is optically inactive. The result has been rationalised in line with the current hypothesis on the origin of carotenoid CD spectra.
标题中提出的问题得到了回答。(3R,3'S)-内消旋玉米黄质进行了碘催化的光化学立体异构化反应。对映体(9Z)和(9'Z)几何异构体通过半制备高效液相色谱法分离,并仅在手性柱上作为非对映体二氨基甲酸盐分离。氨基甲酸盐的裂解无法实现。系统研究了(3R,3'R)-和(3R,3'S)-内消旋玉米黄质几何异构体的(1"S,1"S)-和(1"R,1"R)-二氨基甲酸盐的圆二色光谱,并揭示了氨基甲酸盐部分的贡献。得出的结论是,(9Z,3R,3'S)-“内消旋”-玉米黄质尽管没有对称元素,但却是光学非活性的。这一结果已根据目前关于类胡萝卜素圆二色光谱起源的假设进行了合理说明。