天然一叶萩型生物碱二聚体的仿生合成初步分析-preliminary analysis of biomimetic synthesis of natural securineous alkaloids dimer.docx

暨南大学硕士论文 暨南大学硕士论文 II II 并没有得到相应的目标产物。但意外得到了氧化重排产物与硝酮环分子间加成形成的二 聚体。 （4）本文共合成了 8 个一叶萩型生物碱二聚体和三聚体。化合物都均通过 ESI-MS, HRMS (ESI), 1H NMR, 13C NMR, DEPT-135, 1H-1H COSY, HSQC, HMBC, NOESY 等光谱 方法进行结构鉴定和相对构型的确定。 关键词：一叶萩型生物碱；二聚体；仿生合成；光化学；[2+2]环加成；[2+3]偶极环加 成反应；立体选择性；区域选择性 III III Abstract Objective：Natural securinine alkaloid, which belongs to indole alkaloid, is a kind of alkaloid with special chemical skeleton. Its main types are divided into securinine-type and norsecurine-type alkaloid. Most of securinine alkaloid could easily lead to the formation of dimers, trimers as well as polymers, and show good pharmacological activities. In this thesis, we mainly explore the mechanism of biosynthetic pathways of these dimeric securinine-type alkaloids, and use chemical methods to simulate the biosynthetic pathway to synthesize these dimers, even trimers. Method: (1) [2+2] cycloaddition: Based on the structure analysis of highly axisymmetric securinine alkaloid dimers, it could be explained through the chemical mechanism of [2 + 2] cycloaddition. So we treated securinine- and norsecurinine-type alkaloids under ultraviolet lights to obtain the dimers. Baylis-Hillman reaction: Other kinds of dimers and trimers with special combinational ways were analyzed and could be explained via Baylis-Hillman reaction. Different catalyst (including self-catalyzed) and conditions were also utilized to get this type of dimers and trimers. [2 +3] cycloaddition: According to oxidation rearrangement of previous reports, the same way was also used for securinine dimer by oxidation rearrangement and dipole [2 +3] cycloaddition with another molecule of securinine to get the oxidation rearrangement dimers. Result: (1) In this thesis, a highly regio- and stereoselectivitive securinine alkaloid dimer was synthesized which is exactly the same as the one separated by professor Ye Wencai group. Different kinds of securinine with similar structure were also used to go through [2+2] cycloaddtion reaction and achi