【作者】 刘剑；

【导师】 厍学功；

【作者基本信息】 兰州大学 ， 有机化学， 2009， 博士

【摘要】 本论文完成了大环内酯类天然产物epi-6-Decarestricitine C₁和aspergillides B的对映体的全合成。并对cephalosporolide C、E和F进行了不对称全合成研究，完成了其共同关键中间体的合成，为其全合成奠定了坚实的基础。论文共包括以下四部分内容：一．氧杂六元环（吡喃）的构筑策略及其在天然产物全合成中的应用（综述）简单介绍了近年来吡喃环的构筑策略及其在天然产物全合成中的应用。二．具有抗疟活性的大环内酯epi-6-Decarestricitine C₁的不对称全合成研究简要介绍了decarestricitine类化合物的分离、活性、结构特点以及decarestricitine C的合成背景。采用Sharpless不对称双羟化和Evans aldol反应构筑天然产产物所包含的手性中心，以Mitsunobu反应和RCM反应为关键反应，以12％的总产率简捷高效的完成了具有抗疟活性的天然产物epi-6-decarestricitine C₁的全合成。三．大环内酯类天然产物aspergillides的不对称全合成研究简要介绍了大环内酯类天然产物aspergillide A-C的分离、生理活性、结构特点以及合成背景。探索出了一条简捷高效合成aspergillide B和C的通用路线。采用该路线以五乙酰基半乳糖为起始原料12步9％的总产率简捷高效的完成了（+）-aspergillideB的全合成。四．Cephalosporolide C，E和F的不对称全合成研究简要介绍了Cephalosporolide类化合物的分离、结构特点以及合成背景和Linchpin反应及其在我们组之中的应用。探索出了一条构筑Cephalosporolide类化合物核心骨架的通用策略，并以Linchpin反应为关键步骤完成了合成Cephalosporolide C、E、和F的共同关键中间体的合成，为其全合成奠定了良好的基础。更多还原

【Abstract】 This dissertation aims at the studies on the asymmetric total syntheses ofanti-malarial epi-6-decarestricitine C₁, macrolide （+）-aspergillede B andcephalosporolide C, E and F. It consisted of the following four parts:Chapter 1. The construction of chiral pyran rings and the applications in naturalproducts syntheses （review）The recent development of construction of chiral pyran rings and application innatural products syntheses were briefly reviewed.Chapter 2. Facile total synthesis of anti-malarial epi-6-Decarestricitine C₁The isolation, bioactivity and structures features of decarestricitine family andsynthetic background of decarestricitine C were introduced briefly.A facile and effective synthesis of epi-6-Decarestricitine C₁ has been achievedfrom commercially available （S）-propylene oxide in 12% overall yield. The notablefeature of the synthesis was the use of reaction such as Sharpless assymetricdihydroxylation, aldol addition, Mitsunobu reaction and ring-closing metathesis（RCM）.Chapter 3. Synthetic studies toward aspergillidesThe isolation, bioactivity, structures features and synthetic background ofaspergillide A-C were introduced briefly.A common strategy to synthesis of aspergillide B and C was investigated, whichwas applied to the synthesis of （+）-aspergillide B. Highlights of the synthetic ventureincluded the C-glycosylation reaction when constructing the 2,6-trans-disubstitutedpyrane core, a highly effective four-step sequence without purification to produce the key intermediate and an advantegous E-selective Julia-Kocienski olefination on ahighly elaborate substrate. As for our total synthesis, the longest linear sequencecomprised 12 steps involving a four-step sequence without purification and 9%overall yield.Chapter 4. Synthetic studies toward cephalosporolide C, E and FThe isolation, structures features and synthetic background of cephalosporolidefamily were introduced briefly.The introduction of three-component linchpin coupling reaction and the works ofour group in this area were described briefly.The advanced intermediate to the synthesis of cephalosporolide C, E and F wasachieved, which lay down a solid foundation for their total synthesis. The synthesischaracterized by use of three-component linchpin coupling reaction.更多还原