Systematic Synthesis of Natural Organic Compounds for the Elucidation of Biological Functions.

1.生物活性环烯丙烷类化合物的系统合成(1)彭塞米特和二羟丙戊酸酯的合成以()-京尼平为起始原料，通过一系列官能团的转化，高效地合成了光学活性的潘司米特和二氢呋喃卓酯。(2)丙花素和普鲁米星的合成。以()-京尼平为起始原料，完成了光学活性尿囊素和羽毛菌素的合成。(3)二环内酯类化合物的合成。以京尼平为起始原料，高效地合成了二氢马钱素、苦马钱苷、龙胆苦苷、苦瓜苷、苦瓜苷和沙拉胶。(4)儿茶素的合成。以()-京尼平为原料合成了()-天冬氨酸。通过该合成确定了天然叶柄的绝对结构。(5)尼乙内酯和新马他醇的合成。以京尼平为原料，合成了棉铃虫性引诱剂尼乙内酯和花边翅引诱剂新马他醇。(6)()-Tecomanin的合成。以()-京尼平为原料合成了马钱子素、单萜类生物碱。(&lt；+-减法)-Jolkinolide A，B和E的合成以9-甲氧基碳酰基-1-4，4，10-三甲基-Delta和6-8-八烷酮为原料，合成了Jolkinolide A，B和E。以α-二酮为原料，通过温和的酯化反应和分子内的Wittig-Horner反应合成了一种新的α-亚甲基丁烯内酯。开发新的合成反应。(1)。研究了取代2-甲氧基-1，3-丁二烯的立体选择性合成方法。(2)。通过分子氧、1，3-二酮和烯烃的形式[2 2 2]环加成反应，开发了一种合成环状过氧化氢的新方法。(3)。开发了利用电化学氧化硅取代杂原子化合物的新的合成反应。

1. Systematic Synthesis of Biologically Active Iridoids.(1) Synthesis of Penstemide and Didrovaltrate. Optically active penstemide and didrovaltrate were synthesized very efficiently starting from (+)-genipin by the sequence of functional group transformations. (2) Synthesis of Allamandicin and Plumericin. We have accomplished the synthesis of optically active allamandicin and plumericin starting from (+)-genipin. (3) Synthesis of Seco-iridoids. Seco-loganin, sweroside, kingiside, morronoside, gentiopicroside and sarracenin were synthesized efficiently starting from (+)-genipin. (4) Synthesis of Petiodial. (+)-Pctiodial was synthesized from (+)-genipin. The absolute structure of natural petiodial was determined by this synthesis. (5) Synthesis of Nepetalactol and Neomatatabiol. Nepetalactol, sex attractant for aphid, and neomatatabiol, attractant for lace wing were synthesized from (+)-genipin. (6) Synthesis of (+)-Tecomanin. Tecomanin, monoterpene alkaloid was synthesized from (+)-genipin.2. Synthesis of (<plus-minus>)-Jolkinolide A, B, and E. Jolkinolide A, B, and E were efficiently synthesized from 9-methoxycarbony1-4, 4, 10-trimethyl-DELTA^6-8-octalone through podocalpenone. A new synthetic method of gamma-ylidenbutenolid consisting of mild esterification and succeeding intramolecular Wittig-Horner reaction of alpha-diketone was developed.3. Development of new synthetic reactions. (1). Stereoselective synthesis of substituted 2-methoxy-1, 3-butadienes was developed. (2). New synthetic method of cyclic peroxide consisting of formal [2+2+2] cycloaddition of molecular oxygen, 1, 3-diketone, and olefin was developed. (3). New synthetic reactions utilizing electrochemical oxidation of silicon-substituted heteroatom compounds were developed.