Development of the Environmentally Benign Agrichemicals and Novel Drug Seeds Based on Natural Allelochemicals

1.向日葵中化感物质的合成研究(1)完成了9个天然向日葵醇倍半萜类化合物的对映控制全合成，确定了其绝对结构。(2)以Lewis酸为关键反应，通过碳碳键的形成反应，首次完成了向日葵螺内酯A和C的首次全合成和对映选择性全合成。(3)完成了向日葵中向日葵叶的首次全合成和不对称全合成。本文开发的合成路线方便，解决了供应问题。(4)完成了从短缩青霉菌中分离得到的短链霉菌素A、B和C的对映控制全合成。其中，缩维酮C为首次合成，确定了绝对结构。对合成的化合物包括天然产物进行了生物活性评价。(1)用生菜和提摩太两种植物对合成的天然和非天然化合物的化感活性进行了评价。其中，()-和(-)-向日葵酚A和(-)-向日葵酚C表现出较强的活性。活性最强的化合物为2-甲基-3-苯基肉桂酸。(2)在药理活性方面，()-洋茉莉酚D表现出较强的核因子-kB抑制活性。还需要注意的是，()-灯盏花素A对人结肠癌细胞(HCT-116细胞)显示出很强的细胞毒活性。

1. Syntheteic studies on the allelochemicals isolated from sunflower (Helianthus annuus L. var. SH-222) were performed and the following results were obtained.(1) Enantiocontrolled total syntheses of the nine natural heliannuol sesquiterpenoids were completed and the absolute structures were established.(2) The first and enantioselective total syntheses of heliespirones A and C were accomplished by a Lewis acid-mediated carbon-carbon bond forming reaction as a key reaction step, which is a novel transformation.(3) The first and enantioselective total synthesis of sundiversifolide, which has been isolated from sunflower, was accomplished. The synthetic route developed here is convenient and a problem of the supply was solved.(4) Enantiocontrolled total syntheses of breviones A, B and C, which have been isolated from Penicillium brevicompactum Dierckx, were completed. For brevione C, this is the first synthesis and the absolute structure was established.2. Biological evaluations were investigated for the synthesized compounds including natural products.(1) Allelopathic activites for the natural and unnatural compounds synthesized were evaluated using two plants lettuce and timothy. Of these, (+)-and (-)-heliannuol A and (-)-heliannuol C showed strong activity. The compound with the strongest activity was 2-methyl-3-phenylcinnamic acid.(2) Regarding pharmacological activities, (+)-heliannuol D showed a strong NF-kB inhibitory activity. It also should be noted that (+)-brevione A exhibited a strong cytotoxic activity for HCT-116 cell (human colon tumor cell).