Chemical Studies on Rubiaceous New Type Modified Indole Alkaloids

红花新型修饰吲哚生物碱的化学研究

• 批准号: 63570982
• 负责人: AIMI Norio
• 金额: $ 1.47万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63570982/
• 关键词: Rubiaceae; Uncaria; Ophiorrhiza; Indole Alkaloid; Oxindole Alkaloid; Camptothecin; Pumiloside; Deoxypumiloside; Urcaria属; pumiloside; オキシインドール; アルカロイド; 配糖体; カンプトテシン; 構造決定; 合成; 生合成

New type modified indole alkaloids in Thai Rubiaceous plant, Uncaria salaccensis --- From the titled plant four new seco indole alkaloids of hitherto unknown structure classes were isolated. Their structures were elucidated and synthetic studies were made. Thus the first alkaloid, salacin (US-6) was found to be a D- seco modified oxindole alkaloid which was regarded to be formed through oxidative cleavage of 20,21 enamine type double bond. Total synthesis of -salacin was carried out starting from condensation of oxytryptamine and the corresponding car aldehyde. Second and third alkaloids, US-7 and US-8, belonged to the same structural class as salacin. Attempts of chemical derivation from known natural alkaloids or total synthesis were made. Fourth alkaloid, US-9, was new type C-seco oxindole alkaloid and the structure was found to be 3-oxo-7-hydroxy-3,7-secorhyn- chophylline. Chemical derivation from rhynchophylline or isorhynchophylline proved the relative and absolute stereochemistry.Modified endole alkaloids of Ophiorrhyza pumila of Rubiaceae --- New type modified indole alkaloids, pumiloside and deoxypumiloside, were found in Ophiorrhiza pumila. The stereo structure was proved through synthesis of pumiloside and its isomer at C-3, 3-epipumiloside. These compounds were long postulated and sought for in the nature as the key members in the "Poststrictosamide Biosynthetic Events" that follow the known intermediates, strictosidine and strictosamide. Further detailed study on the constituents of O. pumila gave an acidic gluco alkaloid and the structure was found to be strictosidic acid.

从泰国茜草科植物-对它们的结构进行了鉴定并进行了合成研究。因此，发现第一种生物碱salacin（US-6）是D-开环修饰的氧化吲哚生物碱，其被认为是通过20，21烯胺型双键的氧化断裂形成的。以羟色胺与相应的苯甲醛缩合为起始原料，进行了β-salacin的全合成。第二种和第三种生物碱US-7和US-8与salacin属于同一结构类别。从已知的天然生物碱出发，进行了化学衍生或全合成的尝试。第四类生物碱US-9为新型C-开环羟吲哚生物碱，结构为3-氧代-7-羟基-3，7-开环儿茶素- chophylline。通过对钩藤碱或异钩藤碱的化学衍生，证明了相对和绝对立体化学的存在。从茜草科植物--通过对苦杏仁苷及其C-3，3-表苦杏仁苷异构体的合成，证明了其立体结构.这些化合物被长期假定并在自然界中寻找，作为已知中间体，strictosidine和strictosamide之后的“Poststrictosamide生物合成事件”中的关键成员。进一步详细研究了O. pumila得到酸性葡糖生物碱，发现其结构为异辛酸。

项目成果

N. Aimi, M. Nishimura, A. Miwa, H. Hoshino, S. Sakai, and J. Haginiwa: "Pumiloside and Deoxypumiloside; Plausible Intermediates of Camptothecin Biosynthesis" Tetrahedron Letters Vol. 30, No. 37 4991-4994, 1989.

N. Aimi、M. Nishimura、A. Miwa、H. Hoshino、S. Sakai 和 J. Haginiwa：“普米洛苷和脱氧普米洛苷；喜树碱生物合成的合理中间体”四面体快报卷。

Dhavadee Ponglux et al.: "Structure and Synthesis of Two New Types of Oxindole Alkaloids Found from Uncaria salaccensis" Chemical and Pharmaceutical Bulletin. 38. 573-575 (1990)

Dhavadee Ponglux 等人：“从 Uncaria salaccensis 中发现的两种新型羟吲哚生物碱的结构和合成”化学和药物通报。

Norio Aimi et al.: "Pumiloside and Deoxypumiloside;Plausible Intermediates of Camptothecin Biosynthesis" Tetrahedron Letters. 37. 4991-4994 (1989)

Norio Aimi 等人：“普米洛苷和脱氧普米洛苷；喜树碱生物合成的合理中间体”四面体快报。

D. Ponglux, S. Wongseripipatana, N. Aimi, M. Nishimura, M. Ishikawa, H. Sada, J. Haginiwa, and S. Sakai: "Structure and Synthesis of Two New Types of Oxindole Alkaloids Found from Uncaria salaccensis" Chem. Pharm. Bull., Vol. 38, No. 3 573-575, 1990.

D. Ponglux、S. Wongseripipatana、N. Aimi、M. Nishimura、M. Ishikawa、H. Sada、J. Haginiwa 和​​ S. Sakai：“从钩藤中发现的两种新型羟吲哚生物碱的结构和合成”化学