海星Asterias rollestoni的化学成分研究

海星Asterias rollestoni的化学成分研究

李国强, 邓志威, 李军, 付宏征, 林文翰^*

1.北京大学天然药物及仿生药物国家重点实验室, 北京 100083;
2.青岛科技大学, 青岛 266042;
3.北京师范大学化学分析中心, 北京 100073

收稿日期:2004-01-12 修回日期:2004-05-10 出版日期:2004-06-15 发布日期:2004-06-15
通讯作者: 林文翰*

Chemical Constituents from Starfish Asterias rollestoni

LI Guo-qiang, DENG Zhi-wei , LI Jun, FU Hong-zheng, LIN Wen-han^*

1.State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing 100083, China;
2.Qingdao University of Science and Technology, Qingdao 266042, China;
3.Chemical Test Center, Beijing Normal University, Beijing 100073, China

Received:2004-01-12 Revised:2004-05-10 Online:2004-06-15 Published:2004-06-15
Contact: LIN Wen-han*

摘要/Abstract

摘要： 目的　从青岛海星Asteriasrollestoni分离并确定结构新颖的活性化合物, 并阐明海星中的次生代谢产物的多样性。方法　应用正相和反相色谱包括半制备HPLC方法分离和纯化化合物; 应用IR, UV, MS, 1D和2D NMR, 以及理化性质确定化合物的结构。结果　从青岛海星Asteriasrollestoni中获得17种化学成分, 分别为N7-2'-deoxypseudoxanthosine (1), 2'-O-methyl in osine (2), 2'-deoxyinosine (3), 2'-O-methylguanosine (4), inosine (5); thymine (6), uracil (7), thymidine (8), deoxyuridine (9), 2'-O-methyluridine (10), (-)-(1S, 3S)-1-methyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylicacid (11), (-)-(1R, 3S)-1-methyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylicacid (12), (-)-(3S)-1,2,3,4-tetrahydro-β-carboline-3-carboxylicacid (13), L-tryptophan (14), L-phenylalanine (15), 3-carboxyindole (16)和p-hydroxybenzoicacid (17)。结论　其中1为新化合物。它们的化学结构经1D, 2D NMR, 以及其它波谱分析, 结合与已知化合物的波谱和理化数据对照得以确定。化合物8, 9, 10为首次从天然资源中获得, 化合物14和15系首次从该海星中获得。

关键词: 海星, 海星, 海星, Asteriasrollestoni, Asteriasrollestoni, Asteriasrollestoni, N7-2'-deoxypseudoxanthosine, N7-2'-deoxypseudoxanthosine, N7-2'-deoxypseudoxanthosine

Abstract: Aim　To investigate novel bioactive and structural metabolites from marine organisms. Methods Column chromatography in association with semi-preparative HPLC were used for the isolation of compounds. 1D and 2D NMR, IR, UV, and MS were employed for structure elucidation. Results From the butanol fraction of the 95 % EtOH extract of the starfish Asterias rollestoni, a new compound N7-2’-deoxypseudoxanthosine (1), along with sixteen known compounds, 2’-O-methyl-inosine (2), 2’-deoxyinosine (3), 2’-O-methylguanosine (4), inosine (5) ; thymine (6), uracil (7), thymidine (8), deoxyuridine (9), 2’-O-methyluridine (10), (-)-(1S, 3S)-1-methyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid (11), (-)-(1R, 3S)-1-methyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid (12), (-)-(3S)-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid (13), L-tryptophan (14), L-phenylalanine (15), 3-carboxy indole (16), and p-hydroxybenzoic acid (17), have been isolated. Conclusion Compound 1 is a new natural product, and compounds 8, 9 and 10 are isolated from natural sources for the first time, and the known compounds except 14 and 15 are first reported from starfish Asterias rollestoni .

Key words: starfish, starfish, Asterias rollestoni, Asterias rollestoni, N7-2'-deoxypseudoxanthosine, N7-2'-deoxypseudoxanthosine

中图分类号:

R931.6

R931.77

Supporting: Foundation item: High Tech Research and Development ( 863) Prograrmme of Ministry of Science and Technology of China (2003AA620403, 2002AA217081) , National Natural Science Foundation of China (No. 40176038, 30171106).
^*Corresponding author. Tel.: 010-62062210; fax: 010-82802724

李国强, 邓志威, 李军, 付宏征, 林文翰^*. 海星Asterias rollestoni的化学成分研究[J]. .

LI Guo-qiang, DENG Zhi-wei , LI Jun, FU Hong-zheng, LIN Wen-han^*. Chemical Constituents from Starfish Asterias rollestoni[J]. .

参考文献

[1] Bruno I, Minale L, Riccio R, et al. Marine eicosanoides: occurrence of 8, 11, 12-trihydroxylated eicosanoic acids in starfishes [J]. Chem Rev, 1993, 93 (5): 1862-1889.
[2] Bruno I, Minale L, Riccio R. Starfish saponins, part 50. Steroidal glycosides from the Okinawan starfish Nardoa tuberculata [J]. J Nat Prod, 1993, 56: 1057-1064.
[3] Iorizzi M. Starfish saponins, part 51. Steroidal oligoglycosides from the starfish Distolasterias nippon [J]. J Nat Prod, 1993, 56: 1786-1798.
[4] Marino SD, Palagiano E, Zollo F, Minale L. A novel sulphated steroid with a 7-membered 5-oxalactone B-ring from an antarctic starfish of the family Asteriidae [J]. Tetrahedron, 1997, 53, 8625-8628.
[5] Iorizzi M. Investigation of the polar steroids from an Antarctic starfish of the family Echinasteridae: isolation of twenty seven polyhydroxysteroids and steroidal oligoglycosides, structures and biological activities [J]. Tetrahedron, 1996, 52: 10997-11012.
[6] Iorizzi M. Starfish saponins, part 52. Chemical constituents from the starfish Echinaster brasiliensis [J]. J Nat Prod, 1993, 56: 2149-2162.
[7] Muralikrishna G, Reuter G, Jasna PK, et al. Identification of a new ganglioside from starfish Asterias rubens [J]. Carbohydr Res, 1992, 236: 321-326.
[8] Casapullo A, Finamore E, Minale L, et al. Starfish saponins, part 49. New cytotoxic steroidal glycosides from the starfish Fromia monilis [J]. J Nat Prod, 1993, 56: 105-115.
[9] Findlay JA, He ZQ. Minor saponins from the starfish Asterias forbesi [J]. Can J Chem, 1990, 68: 1215-1217.
[10] Marino SD, Iorizzi M, Zollo F, et al. Isolation, structure elucidation, and biological activity of the steroid oligoglycosides and polyhydroxysteroids from the Antarctic starfish Acodontaster conspicuous [J]. J Nat Prod, 1997, 60: 959-966.
[11] Finamore E, Zollo F, Minale L. Starfish saponins, part 47. Steroidal glycoside sulfates and polyhydroxysteroids from Aphelasterias japonica [J]. J Nat Prod, 1992, 55: 767-772.
[12] Iorizzi M, Minale L, Riccio R. Starfish saponins, part 46. Steroidal and polyhydroxysteroids from the starfish Culcita novaeguineae [J]. J Nat Prod, 1991, 54: 1254-1264.
[13] Iorizzi M, Minale L, Riccio R. Starfish saponins, part 45. Novel sulfated steroidal glycosides from the starfish Astropecten scoparius [J]. J Nat Prod, 1990, 53: 1225-1233.
[14] Zollo F, Finamore E, Martuccio C, et al. Starfish saponins, part 44. Steroidal glycosides from the starfish Pisaster giganteus [J]. J Nat Prod, 1990, 53: 1000-1005.
[15] Iorizzi M, Minale L, Riccio R. Starfish saponins, part 48. Isolation of fifteen sterol constituents (six glycosides and nine polyhydroxysteroids) from the starfish Solaster borealis [J]. J Nat Prod, 1992, 55: 866-877.
[16] Auria MVD, Finamore E, Minale L, et al. Steroids from the starfish Euretaster insignis: a novel group of sulfated 3β, 21-dihydroxysteroids [J]. J Chem Soc Perkin Trans, 1984, 1: 2277-2282.
[17] Marino SD, Iorizzi M, Palagiano E, et al. Starfish saponins, part 55. Isolation, structure elucidation, and biological activity of the steroid oligoglycosides from an Antarctic starfish of the family Asteriidae [J]. J Nat Prod, 1998, 61: 1319-1327.
[18] Hashimoto Y. In marine toxins and other bioactive marine metabolites [M]. Japan: Japan Scientific Societies, Tokyo, 1979, 268-288.
[19] Sproat BS, Beijer B, Iribarren A. New synthetic routes to protected purine 2’-O-methylriboside-3’-O-phosphoramidites using a novel alkylation procedure [J]. Nucleic Acids Res,1990, 18: 41-49.
[20] NorotnyL, Mohammed AH, Hamza H. Inosine and 2’-deoxy-inosine and their synthetic analogues: lipophilicity in relation to their retention in reversed-phase liquid chromatography and the stability characteristics [J]. J Pharm Biomed Anal, 2000, 24: 125-132.
[21] Fu HZ, Zhang XW, Lin WH. Chemical constituents from Chinese Anthopleura xanthogrammica [J]. Chin J Mar Drugs, 1998, 17: 13-16.
[22] Sekine M, Peshakova S, Hata T, et al. A new method for regioselective 2’-O-methylation and its application to the synthesis of 2’-O-methyl-5-[(carboxymethyl) amino methyl]-uridine [J]. J Org Chem, 1987, 52: 5060-5061.
[23] Brossi A, Focella A, Teitel S. Alkaloids in mammalian tissues 3. Condensation of L-tryptophan and L-5-hydroxytryptophan with formaldehyde and acetaldehyde [J]. J Med Chem,1973, 16: 418-420.
[24] Martha W. Merck Index [M]. 9th ed. USA: Merck and Co. Inc, 1976. 1256.
[25] Arai K, Mesuda K, Kiniyama N, et al. Metabolic products of Aspergillus terreus. IV. Metabolites of the strain IFO 8835. (2). The isolation and chemical structure of indolyl benzoquinone pigments [J]. Chem Pharm Bull, 1981, 29: 961-969.
[26] Martha W. Merck Index [M]. 9th ed. USA Merck and Co. Inc, 1976. 636.