Synthetic studies on antitumor active molecules utilizing of sequential cyclizations

对δ-生育三烯醇、科里奥林和紫杉醇等抗肿瘤活性化合物进行了合成研究。本研究提供了以下结果：1)至4)。1)开发了一条新的短步合成δ-生育三烯醇的路线。2)在科里奥林的合成研究过程中，碘化钐(II)引发的级联反应，使双-α，β-δ位含叔丁基二甲基硅氧基的不饱和酯发生还原偶联-Dieckmann缩合反应，生成具有光学活性的双环[3.0]辛烷环体系，并具有区域选择性。3)建立了紫杉醇C环类化合物的立体选择性高效合成路线。4)通过E-和Z-2-甲基-8-氧杂-2-烯二酸二甲酯和Z-二甲基2-甲基-7-氧代-2-烯二酸二甲酯与碘化钐的还原环化、Dieckmann缩合和内酯化反应，分别立体地合成了顺式和反式双环[4.4.0]正十一环和反式双环[4.3.0]正庚环体系，每个体系都由γ-内酯组成。

The synthetic studies on several antitumor active compounds including δ-tocotrienol, coriolin and paclitaxel were performed. The following results, 1) to 4), were provided by this study. 1) A novel and short step synthetic route for δ-tocotrienol was developed. 2) In the course of the synthetic studies on coriolin, samarium (II) iodide-induced cascade reaction involving reductive coupling-Dieckmann condensation of bis-α, β-unsaturated esters bearing tert-butyldimethylsilyloxy group at δ-position to highly diastereo- and regioselectively produce bicyclo [3. 3. 0] octane ring systems in optically active form. 3) A stereoselective and efficient synthetic route for the C ring system of paclitaxel was developed. 4) Cascade reaction involving reductive cyclization, Dieckmann condensation, and lactonization of E- and Z-dimethyl 2-methyl-8-oxoundec-2-enedioates and Z-dimethyl 2-methyl-7-oxodec-2-enedioate with samarium (II) iodide was found to stereospecifically produce cis and trans bicyclo [4. 4. 0] decane ring systems and trans bicyclo[4.3.0]nonane ring system each consisting of γ-lactone, respectively.