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Synthetic Studies on Ring-Fused Macrocyclic Terpenoids

稠环大环萜类化合物的合成研究

基本信息

批准号：
11672132
负责人：
KODAMA Mitsuaki
金额：
$ 0.58万
依托单位：
Tokushima Bunri University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

This project aimed to synthesize novel Terpenoids having ring-fused macrocyclic skeleton, especially trinervitane diterpenoids with tricyclo[7.2.0^<1.16>] hexadecane carbocycle.1. By applying kinetic resolution of (±)-4-methyl-Hajos-Parrish ketone using baker's yeast reduction, optically pure (R)-2,6-dimethylbicyclo[4.3.0]nona-l-ene-3,7-dione was obtained in good yield. By controlling the reaction time, it was possible to obtain the enantiomer in high optical purity.2. Synthesis of trinervitane diterpene was examined. Starting from (R)-2,6-dimethylbicyclo[4.3.0]nona-l-ene-3,7-dione described above, various compounds with requisite side chains and oxygen functionarities were prepared. However, attempted formation of the third 11-menbered ring was unsuccessful in almost cases. The desired tricyclic compound was oobtained only by the intramolecular alkylation of a-sulfenyl anion in low yield.3. Stereoselective synthesis of glabrescol, a novel mneso-type triterpene with five continuously linked tetrahydrofuran rings, was investigated. By applying baker' yeast reduction, asymmetric epoxidation, and asymmetric dihydroxylation as chilarity induction method, a compound having the structure reported for glabrescol was synthesized. But the spectral data were not identical to those of the natural product. Comparison of NMR spectra of Natural and synthetic compounds suggested that the stereochemistry around the central part of molecule is different. However, synthesized meso-compound with different configuration at the central THF ring was not identical to the natural product again. Thus, we could point out that the reported structure of glabrescol is incorrect. But, we could not propose the correct structure.

本项目旨在合成具有大环稠合骨架的新型萜类化合物，特别是具有三环[7.2.0^&lt；1.16；]十六烷碳环的三环维生素二萜1。通过面包酵母还原反应动力学拆分(±)-4-甲基-Hajos-Parrish酮，以较好的产率获得了光学纯的(R)-2，6-dimethylbicyclo[4.3.0]nona-l-ene-3，7-dione。通过控制反应时间，可以得到光学纯度较高的对映体。对三环维生素二萜的合成进行了研究。从上述(R)-2，6-dimethylbicyclo[4.3.0]nona-l-ene-3，7-dione出发，制备了具有所需侧链和氧官能团的各种化合物。然而，尝试形成第三个11-膜环在大多数情况下都是失败的。目标三环化合物仅通过α-亚硫基阴离子分子内烷基化反应，产率较低。研究了一种新型四氢呋喃四氢呋喃连环三萜化合物--光滑酚的立体选择性合成。采用面包酵母还原、不对称环氧化和不对称双羟基化作为辣味诱导方法，合成了具有文献报道的光滑醇结构的化合物。但光谱数据与天然产物的光谱数据并不相同。天然化合物和合成化合物的核磁共振波谱比较表明，分子中心附近的立体化学有所不同。然而，合成的中心四氢呋喃环上不同构型的介孔化合物与天然产物并不完全相同。因此，我们可以指出已报道的光滑醇的结构是不正确的。但是，我们无法提出正确的结构。