【作者】 张伟伟；

【导师】 厍学功；

【作者基本信息】 兰州大学 ， 化学·有机化学， 2019， 博士

【摘要】 本论文首先采用Staudinger烯酮[2+2]环加成反应对Calyciphylline A类虎皮楠生物碱中特有的6,6,5,7-四环骨架进行了构筑研究,为Calyciphylline A类虎皮楠生物碱的合成提供新的合成策略和思路;同时,从商业可得的色胺盐酸盐为起始原料,通过Diles-Alder反应串联分子内的酰胺化和二碘化钐促进的自由基环化为关键反应以8%的总收率完成了Aspidofractinine类吲哚生物碱Paucidirinine的全合成,并对相关生物碱Pauciduridine进行了不对称合成研究。全文共包含如下三章:第一章:基于吲哚骨架的环加成和烷基化反应在合成吲哚生物碱中的应用(综述)。简要介绍了基于吲哚骨架的环加成反应和烷基化反应在吲哚生物碱合成中的大量应用实例。综述最后部分,对这两种合成策略未来在吲哚生物碱中的发展做了展望。第二章:Calyciphylline A类虎皮楠生物碱6,6,5,7-四环骨架的构筑研究简要介绍了Calyciphylline A类虎皮楠生物碱的分离以及全合成工作进展。在前人工作的基础上提出了一种合成Calyciphylline A类虎皮楠生物碱6,6,5,7-四环骨架的新策略,尝试了经典的Staudinger烯酮[2+2]环加成反应,四级联烯亚胺以及联二烯的[2+2]环加成反应,该工作目前还在继续探索中。第三章:Aspidofractinine类吲哚生物碱Paucidirinine及其相关生物碱的全合成研究简要介绍了Aspidofractinine类吲哚生物碱的分离,及其合成进展。采用亚胺互变异构成烯胺,随后串联分子内的[4+2]环加成和酰胺化反应,二碘化钐促进的自由基环加成反应完成了Paucidirinine的消旋全合成。同时,又对Pauciduridine进行了不对称合成研究。更多还原

【Abstract】 This thesis first studied the strategy to construct 6,6,5,7-tetracyclic skeleton of Calyciphylline A-type Daphniphyllum alkaloids which utilized[2+2]reaction of Staudinger ketene,provided a new strategy and idea for the Daphniphyllum synthesis.At the meantime,starting from commercial available tryptamine hydrochloride,using the cascade reaction of Diles-Alder reaction,intramolecular amidation and SmI₂promoted radical cyclization reaction as key step,we finished the total synthesis of Aspidofractinine indole alkaloid Paucidirinine with 8%overall yield and then conducted asymmetric synthesis studies of Pauciduridine.The full text contains the following three chapters:Chapter 1.Applications of Cycloadditions and Alkylations Based on Indole Skeleton（Review）.This chapter introduces various reactions forms of cycloadditions and alkylations which based on indole skeleton,while presents serveral examples concerns the synthesis application of those reaction.Finally we made prospect of future development of these reactions.Chapter 2.Studies towards Constructions of 6,6,5,7-Tetracyclic Skeleton of Calyciphylline A-type Daphniphyllum Alkaloid.This chapter introduces general information of Daphniphyllum alkaloid,and progress in synthesis of Daphniphyllum alkaloid,especially the Calyciphylline A-type Daphniphyllum alkaloid.On the basis of the previous work,a new strategy for synthesis of 6,6,5,7-tetracyclic skeleton is proposed.The classical Staudinger Ketene Cycloaddition and[2+2]reaction of allene and quaternary allene imine were also explored,this part of work is still under exploring.Chapter 3.Studies on Total Synthesis of Paucidirinine and Related Aspidofractinine Indole Alkaloids.A brief introduction of Aspidofractinine’s general information and review of previous synthesis works was first presented in this chapter,then we conduct our total synthesis using synthetic strategy which constructed the crucial scaffold of Paucidirinine via[4+2]cycloaddition,amidation and samarium diiodide-promoted radical cyclization.The asymmetric synthesis of Pauciduridine is now under studying.更多还原