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题名: 虎皮楠科生物碱和楝科四降三萜化学成分研究
作者: 邸迎彤
学位类别: 博士
答辩日期: 2007-01-23
授予单位: 中国科学院昆明植物研究所
授予地点: 昆明植物研究所
导师: 郝小江
关键词: 虎皮楠科 ; 楝科 ; 生物碱 ; 四降三萜 ; 核磁共振 ; 密度函数理论
学位专业: 植物学
中文摘要: 本论文对虎皮楠科 (Daphniphyllaceae) 植物,两个产地的牛耳枫(Daphniphyllum calycillum Benth)(分别采自云南西双版纳和广东鼎湖山), 长序虎皮楠(Daphniphyllum longeracemosum Rosenth),和云南虎皮楠(Daphniphyllum yunnanense C. C. Huang)的生物碱成分,以及楝科 (Meliaceae) 浆果楝属植物灰毛浆果楝(Cipadessa cinerascens (Pell.) Hand.-Mazz)的化学成分进行分离。从三种虎皮楠科植物中共分离鉴定了 52 个生物碱成分,其中新化合物 21 个。从灰毛浆果楝中共分离鉴定了 15 个化合物,其中新化合物 7 个。包括六个四降三萜和一个21碳烯类化合物。 第一章牛耳枫(Daphniphyllum calycillum Benth)(产自云南西双版纳)的生物碱成分研究。从其枝叶提取物的粗碱部分分离鉴定了 13 个生物碱,其中有4个新化合物。化合物 1 为一个具有新颖重排骨架的虎皮楠生物碱,该生物碱在溶液中体现为多个构象异构体互变平衡的产物。通过化学、晶体学、计算、以及热动力学方法证实了构型异构体的存在与其结构,以及它们之间的互变关系。 第二章牛耳枫(Daphniphyllum calycillum Benth)(产自广东鼎湖山)的生物碱成分研究。从其枝叶提取物的粗碱部分分离鉴定了九个生物碱,其中化合物 14(calycilactone A)为一个具有新颖的六环骨架的生物碱,我们推测其生源上可能是通过具有 daphnilactone B 骨架的前体发生pinacol rearrangement 得到的。 第三章为长序虎皮楠 (Daphniphyllum longeracemosum Rosenth)的生物碱成分研究。从其枝叶提取物的总碱部分分离鉴定了 15 个生物碱,其中,Longeracinphyllin B 为新颖的断-10,17-longeracinphyllin A (24) 型骨架的虎皮楠生物碱。Longphyllinesides A–D(25–28)为另一类新颖的虎皮楠生物碱, 生源上由longeracinphyllin A 类生物碱的异戊二烯基和环烯醚萜deacetylasperuloside 的烯醚键通过 Diels-Alder 反应形成的。通过计算化学方法,对Longphyllinesides A–C 加成的立体选择性的控制因素进行研究。计算结果显示该反应可能无需在酶的催化下即可实现高度立体选择性加成。 第四章为云南虎皮楠(Daphniphyllum yunnanense C. C. Huang)的生物碱成分研究。从其枝叶提取物的粗碱部分分离鉴定了 15 个生物碱,其中 10 个新化合物。新化合物 3843 具为 Yuzurimine 型骨架;新化合物 4446 为具有 Daphnane 型骨架 C-30 生物碱;新化合物 47 为具有 secodaphnane 型骨架 C30 生物碱。Yunnandaphninines C 和 D 是从 yuzurimine 类生物碱向 calyciphylline A 类生物碱转化的关键中间体。这两个生物碱的发现确证了两类骨架之间的生源关系。 第五章为灰毛浆果楝(Cipadessa cinerascens (Pell.) Hand.-Mazz)四降三萜化学成分研究。从其叶子提取物中分离鉴定了15 个化合物,其中有7个为新化合物(化合物53-59)。从该属中分离得到的其他化合物类型包括二十一碳烯类化合物、二萜、酚类、甾体和甾体苷。 第六章综述了天然产物中 Diels-Alder 反应研究进展。总结了天然产物生源途径中是否含 Diels-Alder 反应的判断方法。反应是否需要在相应的 Diels-Alderase 催化的判断方法及其验证方法。此外还综述了天然的和人工Diels-Alderase 催化机制。参考文献 39 篇。
英文摘要: This thesis elaborated the studies on the alkaloids of daphniphyllum plants, Daphniphyllum calycillum Benth (collected in Xishuangbanna of Yunnan province and Dinghu Mountain in Guangdong province, respectively), Daphniphyllum longeracemosum Rosenth, and Daphniphyllum yunnanense C. C. Huang, and on chemical constitutes of Cipadessa cinerascens. By a variety of chromatography over various materials, 65 compounds, including 28 new ones, were isolated, which mainly covered daphniphyllum alkaloids with various skeleton and tetranortriterpenoids. Their structures were mainly elucidated on the basis of spectroscopic studies. Chapter 1 Studies on alkaloids of Daphniphyllum calycillum Benth (collected in Xishuangbanna of Yunnan province) Thirteen Daphniphyllum alkaloids, including five new ones, were isolated and elucidated from rough alkaloids part of leaves and twigs of Daphniphyllum calycillum Benth. Among them, compound 1 was a novel one with rearranged skeleton. Broading signals, which were observed in 1D-NMR spectra, suggested that several interconverted conformational isomers of 1 might equilibrate in solution. By spectral, crystallographic, chemical, thermodynamic, and computational means, we elucidated structures of its three interconverting conformers. Chapter 2 Studies on alkaloids of Daphniphyllum calycillum Benth (collected in Dinghu mountain in Guangdong province) Eight Daphniphyllum alkaloids, including a new one (calycilactone A), were isolated and elucidated from rough alkaloids from leaves of Daphniphyllum calycillum Benth. Calycilactone A (1) is a new hexacyclic daphniphyllum one with novel skeleton. Biogenetically, compound 1 originated from daphnilactone B by pinacol rearrangement. Chapter 3 Studies on alkaloids of Daphniphyllum longeracemosum Rosenth Investigation of alkaloid constituents of Daphniphyllum longeracemosum Rosenth has resulted in the isolation of fifteen compounds. And six were new ones. Among them, longeracinphyllin B was a novel daphniphyllum alkaloid with seco-10,17-longeracinphyllin A skeleton; and longeracinesides A–D (25–28) were the other type of alkaloids. Compounds 25–28 may be visualized as cycloadducts of corresponding Daphniphyllum C-21 alkaloids and deacetylasperuloside via intermolecular Diels-Alder reaction. Stereoselectivity of cycloaddition was studied by computational methods, and it was suggested that no enzyme were involved in the high stereo-selectivity reaction. Chapter 4 Studies on alkaloids of Daphniphyllum yunnanense C. C. Huang In this work, fifteen alkaloids, including ten new ones, were isolated from leaves and twigs of Daphniphyllum yunnanense C. C. Huang. Among them, Yunnandaphninines C and D were the key intermediates, connecting two types of alkaloids: yuzurimine and calyciphylline A. Chapter 5 Studies on tetranortriterpenoids of Cipadessa Cinerascens (Pell.) Hand.-Mazz Seven tetranortriterpenoids and eight the other types of natural products, isolated from leaves of Cipadessa cinerascens (Pell.) Hand.-Mazz, were reported in this chapter. Six new tetranortriterpenoids were isolated, which might be originated from a cipadesin-A-type tetranortriterpenoid via pinacol rearrangement. Chapter 6 Review Advances research of Diels-Alder reaction in the biosynthesis of natural products was reviewed.
语种: 中文
内容类型: 学位论文
URI标识: http://ir.kib.ac.cn/handle/151853/138
Appears in Collections:昆明植物所硕博研究生毕业学位论文_学位论文

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虎皮楠科生物碱和楝科四降三萜化学成分研究.邸迎彤[d].中国科学院昆明植物研究所,2007.20-25
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