STEREOSPECIFIC SYNTHESES AND SPECTROSCOPIC PROPERTIES OF ISOMERIC 2,4,6,8-UNDECATETRAENES - NEW HYDROCARBONS FROM THE MARINE BROWN ALGA-GIFFORDIA-MITCHELLAE .4.
STEREOSPECIFIC SYNTHESES AND SPECTROSCOPIC PROPERTIES OF ISOMERIC 2,4,6,8-UNDECATETRAENES - NEW HYDROCARBONS FROM THE MARINE BROWN ALGA-GIFFORDIA-MITCHELLAE .4.
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DOI：
10.1002/hlca.19870700415
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发表时间：
1987-01-01
影响因子：
1.8
通讯作者：
FEIGEL, M
中科院分区：
文献类型：
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作者：
BOLAND, W;SIELER, C;FEIGEL, M
Giffordene（=（2 Z，4 Z，6 E，8 Z）-2，4，6，8-undecatetraene; 9 f）和5个立体异构体是从海洋棕藻Giffordia mitchellae中分离得到的新的C11 H16烃类化合物。它们的合成基于（E）-2-烯醛与适当的炔属正膦的非立体选择性Wittig反应和随后所得（E/Z）-对的色谱分离。然后用Zn（Cu/Ag）在aq.室温下的MeOH给出了新四烯的~（13）C和~ 1H-NMR数据。生物合成，吉福烯（9 f）来源于十二碳-3，6，9-三烯酸，通过不稳定的（3 Z，5 Z，8 Z）-1，3，5，8-十一碳四烯，然后通过热允许的对面1，7-σ迁移氢转移到（2 Z，4 Z，6 E，8 Z）-异构体9 f。
Giffordene (= (2Z,4Z,6E,8Z)-2,4,6,8-undecatetraene; 9f) and five stereoisomers are new C11H16 hydrocarbons from the marine brown alga Giffordia mitchellae. Their synthesis is based on non-stereoselective Wittig reactions of (E)-2-alkenals with appropriate acetylenic phosphoranes and subsequent chromatographic separation of the resulting (E/Z)-pairs. The uniform eynes (> 98% purity) are then stereospecifically reduced to (Z)-alkenes with Zn(Cu/Ag) in aq. MeOH at r.t. 13C and 1H-NMR data of the new tetraenes are presented. Biosynthetically, giffordene (9f) originates from dodeca-3,6,9-trienoic acid via an untable (3Z,5Z,8Z)-1,3,5,8-undecatetraene followed by a thermally allowed antarafacial 1,7-sigmatropic hydrogen shift to the (2Z,4Z,6E,8Z)-isomer 9f.