杀虫活性倍半萜的合成及先导化合物的优化研究

The number of dihydroagrofuran sesquiterpenes are large (at least 600 kinds) and they have the biological activities (such as anti- cancer, anti- decrepitude etc.). However, the constructions of polyol and tetrahydrofuran moiety have the big challenge, so few synthetic chemists can carry out this tough work. Starting from santonin, we developed a new and convenient approach for synthesis of dihydroagrofuran sesquiterpenes and accomplished natural (+)─2,14─ Deoxyalatol dihydroagrofuran sesquiterpene through some important steps, which included the rearrangement of epoxides by alkali, the oxidation on C8, tetrahydrofuran ring cyclization, dihydroxylation on C8, C9, decarbonyl on C12 by Huang MinLon reduction and introduction a hydroxyl on C1. By a series' organic functional groups transformations, we design to synthesize more than thirty dihydroagrofuran sesquiterpenes. In addition, an important rearrangement reaction of enol ester epoxide was found to give a one-step procedure for the construction of naturally occurring isodaucane sesquiterpenes in the presence of a catalyzed amount of Lewis acids. Futhermore, in the process of the dihydroagrofuran sesquiterpenes synthesis, a novel, efficient and highly selective method for deprotecting benzyl and benzylidene acetal groups was developed. 10 articles have been published in the domestic and international journals. A patent had already invented and the review process is in progress.To develop and enrich the new synthetic method of sesquiterpenes, this program has the importance in synthetic chemistry, and the synthetic method has certain practical employment value for the related industry. It also has the patential social and economic values to develop the new and low-toxic pesticide.

以山道年为原料，探索多羟基二氢沉香呋喃倍半萜的合成方法并合成该类化合物。按照组合化学原理，通过酰化合成一系列不同脂基的化合物。经生物活性测试优化具有开发研究价值的杀虫活性先导化合物。本项目对开辟新的萜类合成方法和丰富组合化学研究具有重要的学术意义，对创制研究新型低毒农药、开发国民经济具有潜在的社会经济价值。