Ⅰ.宣威乌头中生物碱成分的研究 Ⅱ.紫杉醇类似物的合成研究Ⅸ.去甲二萜生物碱转化合成紫杉醇类似物的研究
摘要
本论文研究内容共分为两个部分。第一部分为宣威乌头(Aconitum nayzarum var. lasiandrum)中的生物碱成分研究，主要针对极性较大的正丁醇提耳义部位进行分离；第二部分为去甲二萜生物碱转化合成紫杉醇类似物的研究，其中主要涉及C_7-C_(17)键裂解的去甲二萜生物碱的A环修饰，B环扩环和C-7／C-8位功能化以及C环C-12位功能化和14-酮的Baeyer-Villiger氧化反应研究。此外，还探讨了去甲二萜生物碱的O-去甲基化及与HNO_2反应的特殊反应性。(一) 宣威乌头中的生物碱成分研究
从宣威鸟头块根的正丁醇提取部位分离得到14个单体化合物，并用氢谱，碳谱，二维核磁共振谱，质谱以及红外光谱对其结构进行了鉴定，其中3个为新的去甲二萜生物碱，命名为francheline(1)、宣威宁lasianine(2)和宣威生(lasiansine)(3)。11个已知生物碱：16-表-热解乌头宁(16-epi-pyroaconine)(4)，尼奥宁(neoline)(5)，塔拉萨敏(talatisamine)(6)，isotalatizidine(7)，查斯曼宁(chasmanine)(8)，15α-羟基尼奥宁(15α-hydroxyneoline)(9)，1-表-乌头宁(1-epi-aconine)(10)，songoramine(11)12-epi-19-dehydro-napelline(12)，宋果灵(songorine)(13)和12-epi-napelline(14)。lasianine是迄今发现的含8-NH_2的第3个天然产的乌头碱型C_(19-)二萜生物碱。16-表-热解乌头宁(16-epi-pyroaconine)(4)和1-表-乌头宁(1-epi-aconine)(10)是首次从该植物中分得的成分。
(二)去甲二萜生物碱转化合成紫杉醇类似物的研究
1．C_7-C_(17)键裂解的去甲二萜生物碱的A环修饰
以塔拉萨敏为原料，裂解C_7-C_(17)键后，分别设计了A坏修饰的三条路线，即裂解N-C_(19)、N-C_(17)或C_4-C_(19)键。用HIO_4或LTA氧化22和23未能得到N-C_(19)键裂解产物，由于底物无6-OCH_3导致N-C_(19)键裂解后生成的19-醛基不能被及时捕获形成γ-内酯，进而产生了多种可能的反应。希望利用中间体A的
In this dissertation the following two sections are included. 1. Investigation on the phytochemistry of the plant Aconitum nagarum var. lasiandrum. Fourteen diterpenoid alkaloids have been isolated from the crude n-2-butanol extracts of the root of this plant, three of which were new C_(19)-diterpenoid alkaloids. They are francheline (1), lasianine (2), and lasiansine (3). The remained known alkaloids are 16-epi-pyroaconine (4), neoline (5), talatisamine (6), isotalatizidine (7), chasmanine (8), 15α-hydroxyneoline (9), 1-epi-aconine (10) , songoramine (11), 12-epi-19-dehydronapelline (12), songorine (13) and 12-epi-napelline (14). The structures of new alkaloids were elucidated on the basis of spectral methods (~1H NMR, ~(13)C NMR, 2D-NMR, HR-MS, and IR).
Lasianine is the third naturally-occuring aconitine-type diterpenoid alkaloid with an 8-NH2. In addition, 16-epi-pyroaconine(4) and 1-epi-aconine(10) were isolated from the plant for the first time.
2. Studies on the conversion of the norditerpenoid alkaloids into taxoids. On the basis of our previous work on the conversion of the norditerpenoid alkaloids into taxoids, this dissertation described the further research on the modification of ring A in 7,17-seco compounds. In the conversion strategy II, we studied the key reactions related to ring B, including the enlargement of ring B and functionalization at C_7 and C_8. In studies on the key reactions related to ring C, we investigated the functionalization at C_(12) and Baeyer-Villiger oxidation of 14-keto compounds. In addition, we investigated deoxymethylation and the reaction of norditerpenoid alkaloids with HNO2.
In researches of the modification of ring A, with starting from talatisamine, we have designed three routes: the cleavage of N-C_(19), N-C_(17), and C_4-C_(19) bonds.
从宣威鸟头块根的正丁醇提取部位分离得到14个单体化合物，并用氢谱，碳谱，二维核磁共振谱，质谱以及红外光谱对其结构进行了鉴定，其中3个为新的去甲二萜生物碱，命名为francheline(1)、宣威宁lasianine(2)和宣威生(lasiansine)(3)。11个已知生物碱：16-表-热解乌头宁(16-epi-pyroaconine)(4)，尼奥宁(neoline)(5)，塔拉萨敏(talatisamine)(6)，isotalatizidine(7)，查斯曼宁(chasmanine)(8)，15α-羟基尼奥宁(15α-hydroxyneoline)(9)，1-表-乌头宁(1-epi-aconine)(10)，songoramine(11)12-epi-19-dehydro-napelline(12)，宋果灵(songorine)(13)和12-epi-napelline(14)。lasianine是迄今发现的含8-NH_2的第3个天然产的乌头碱型C_(19-)二萜生物碱。16-表-热解乌头宁(16-epi-pyroaconine)(4)和1-表-乌头宁(1-epi-aconine)(10)是首次从该植物中分得的成分。
(二)去甲二萜生物碱转化合成紫杉醇类似物的研究
1．C_7-C_(17)键裂解的去甲二萜生物碱的A环修饰
以塔拉萨敏为原料，裂解C_7-C_(17)键后，分别设计了A坏修饰的三条路线，即裂解N-C_(19)、N-C_(17)或C_4-C_(19)键。用HIO_4或LTA氧化22和23未能得到N-C_(19)键裂解产物，由于底物无6-OCH_3导致N-C_(19)键裂解后生成的19-醛基不能被及时捕获形成γ-内酯，进而产生了多种可能的反应。希望利用中间体A的
In this dissertation the following two sections are included. 1. Investigation on the phytochemistry of the plant Aconitum nagarum var. lasiandrum. Fourteen diterpenoid alkaloids have been isolated from the crude n-2-butanol extracts of the root of this plant, three of which were new C_(19)-diterpenoid alkaloids. They are francheline (1), lasianine (2), and lasiansine (3). The remained known alkaloids are 16-epi-pyroaconine (4), neoline (5), talatisamine (6), isotalatizidine (7), chasmanine (8), 15α-hydroxyneoline (9), 1-epi-aconine (10) , songoramine (11), 12-epi-19-dehydronapelline (12), songorine (13) and 12-epi-napelline (14). The structures of new alkaloids were elucidated on the basis of spectral methods (~1H NMR, ~(13)C NMR, 2D-NMR, HR-MS, and IR).
Lasianine is the third naturally-occuring aconitine-type diterpenoid alkaloid with an 8-NH2. In addition, 16-epi-pyroaconine(4) and 1-epi-aconine(10) were isolated from the plant for the first time.
2. Studies on the conversion of the norditerpenoid alkaloids into taxoids. On the basis of our previous work on the conversion of the norditerpenoid alkaloids into taxoids, this dissertation described the further research on the modification of ring A in 7,17-seco compounds. In the conversion strategy II, we studied the key reactions related to ring B, including the enlargement of ring B and functionalization at C_7 and C_8. In studies on the key reactions related to ring C, we investigated the functionalization at C_(12) and Baeyer-Villiger oxidation of 14-keto compounds. In addition, we investigated deoxymethylation and the reaction of norditerpenoid alkaloids with HNO2.
In researches of the modification of ring A, with starting from talatisamine, we have designed three routes: the cleavage of N-C_(19), N-C_(17), and C_4-C_(19) bonds.
引文
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