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研究生:林俊州
研究生(外文):Jyun-jhou Lin
論文名稱:叢羽軟珊瑚Cespitulariasp.之新奇環內酯雙萜類成份研究
論文名稱(外文):Studies on the Novel Diterpenoids of the Formosan Soft Coral Cespitularia sp.
指導教授:沈雅敬沈雅敬引用關係
指導教授(外文):Ya-ching Shen
學位類別:碩士
校院名稱:國立中山大學
系所名稱:海洋生物科技暨資源學系研究所
學門:自然科學學門
學類:海洋科學學類
論文種類:學術論文
論文出版年:2006
畢業學年度:94
語文別:中文
論文頁數:66
中文關鍵詞:叢羽軟珊瑚
外文關鍵詞:Cespitularia
相關次數:
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  • 收藏至我的研究室書目清單書目收藏:1
臺灣綠島產軟珊瑚Cespitularia sp.的萃取物,以矽膠管柱層析,
葡聚醣凝膠(Sephadex LH-20),及正、逆相高壓液相層析儀進行分離純化,得到五個新的化合物G8-7-7-A (1)、G8-9-15-30-A (2)、G8-10-B(3)、G8-7-6-A (4)、G8-7-5-A (5)。這五個化合物(1-5)皆是具有C-16,C-17, C-19 三支甲基的雙萜類化合物,以及C-4, C-18 環外雙鍵。化合物1 和2 是norditerpene 骨架,具雙圓環。G8-7-7-A (1)是由6, 13 圓環組成,C-7, C-8 間有環內雙鍵,C-6 醇基取代,C-10, C-11間以lactone 環連結,且C-12 有酮基取代。G8-9-15-30-A (2)之基本構形與G8-7-7-A (1)相似,但環內雙鍵位移為C-8, C-9 間,lactone 環轉為C-10, C-12 之間連結,且C-11 變為酮基,故其為6, 14 圓環組成。
化合物3-5 為diterpene 之verticillane 骨架,具三圓環,為5,6, 12圓環組成。G8-10-B (3)於C-7, C-8 有環內雙鍵,C-6 為醇基取代,在C-10 存在hemiacetal,並與C-20 以氧橋的方式連結,C-11, C-12 間則帶有epoxide ring,另外C-20 則有乙酸酯官能基(acetoxy group)。G8-7-6-A (4)結構與G8-10-B (3)幾乎相同,差別只在C-20 官能基取代為丙烯酯(acrylic ester)。G8-7-5-A (5)與G8-10-B (3)基本構形亦相同,差別只在C-6 為酮基,C-20 為酯基,C-11, C-12 間為環內雙鍵連結。
這五個化合物(1-5),分別以質譜、紅外線光譜及1D、2D 核磁共
振圖譜分析,以確認結構。
Five new compounds were isolated from the soft coral Cespitularia sp.collected in Green Island, Taiwan. They are G8-7-7-A (1), G8-9-15-30-A(2), G8-10-B (3), G8-7-6-A (4) and G8-7-5-A (5). All of them belong to diterpenes with three methyl groups at C-16, C-17 and C-18, and an
exocyclic double bond between C-4 and C-18.
Compounds 1 and 2 are bicycle norditerpenes. G8-7-7-A (1)
possesses a 6/13 ring and has an endocyclic double bond between C-7 and C-8. It also contains a hydroxyl group at C-6, a ketone group at C-12 and a lactone ring between C-10 and C-11. G8-9-15-30-A (2) is different from 1 at the lactone ring position. The lactone ring of 2 is between C-10 and C-12, and the ketone group is at C-11. So compound 2 possesses a 6/14 bicyclic ring system.
Compounds 3-5 are cespitularin diterpenes, which belong to a 5/6/12 tricyclic ring. They all have an endocyclic double bond between C-7 and C-8. G8-10-B (3) contains an α-hydroxy-β,γ-epoxy-δ-acetoxy furan and a hydroxyl group at C-6. The only difference between compounds 3 and 4 are substiuents at C-20. The C-20 position of 4 is an acrylic group, while compound 3 has an acetoxyl group at C-20. G8-7-5-A (5) contains an γ-hydroxy-α,β-unsaturated-γ-lactone function and a ketone group at C-6. Their structures were elucidated by mass, IR, 1D and 2D NMR spectroscopic analysis.
目錄
頁次
壹、緒論1
一、前言1
二、Cespitularia 屬珊瑚之天然物文獻回顧3
三、研究動機及目的9
貳、軟珊瑚Cespitularia sp. 之化學成分研究10
一、材料採集10
二、軟珊瑚Cespitularia sp. 之分類地位10
三、軟珊瑚Cespitularia sp. 之萃取與分離流程11
四、軟珊瑚Cespitularia sp. 之分離純化流程13
1. G8-7-7-A (1) 之分離純化流程13
2. G8-9-15-30-A (2) 之分離純化流程15
3. G8-10-B (3) 之分離純化流程17
4. G8-7-6-A (4) 之分離純化流程19
5. G8-7-5-A (5) 之分離純化流程21
五、軟珊瑚Cespitularia sp. 雙萜類成分之結構解析23
1. G8-7-7-A (1) 之結構解析23
2. G8-9-15-30-A (2) 之結構解析34
iv
3. G8-10-B (3) 之結構解析45
4. G8-7-6-A (4) 之結構解析55
5. G8-7-5-A (5) 之結構解析64
參、結論74
肆、參考文獻78
伍、附錄-儀器及材料84

圖目錄
頁次
流程圖一、軟珊瑚Cespitularia sp. 之分離流程12
圖一、化合物1 之光譜資料圖24
圖二、化合物1 之NOESY 立體圖26
圖三、G8-7-7-A (1) 之1H-NMR 圖譜28
圖四、G8-7-7-A (1) 之13C-NMR 及DEPT 圖譜29
圖五、G8-7-7-A (1) 之HMQC 圖譜30
圖六、G8-7-7-A (1) 之HMBC 圖譜31
圖七、G8-7-7-A (1) 之COSY 圖譜32
圖八、G8-7-7-A (1) 之NOESY 圖譜33
圖九、化合物2 之光譜資料圖35
圖十、化合物2 之NOESY 立體圖36
圖十一、G8-9-15-30-A (2) 之1H-NMR 圖譜38
圖十二、G8-9-15-30-A (2) 之13C-NMR 及DEPT 圖譜39
圖十三、G8-9-15-30-A (2) 之HMQC 圖譜40
圖十四、G8-9-15-30-A (2) 之HMBC 圖譜41
圖十五、G8-9-15-30-A (2) 之COSY 圖譜42
圖十六、G8-9-15-30-A (2) 之NOESY 圖譜43
圖十七、化合物3 之光譜資料圖46
圖十八、化合物3 之NOESY 立體圖48
圖十九、G8-10-B (3) 之1H-NMR 圖譜49
圖二十、G8-10-B (3) 之13C-NMR圖譜50
圖二十一、G8-10-B (3) 之HMQC 圖譜51
圖二十二、G8-10-B (3) 之HMBC 圖譜52
圖二十三、G8-10-B (3) 之COSY 圖譜53
圖二十四、G8-10-B (3) 之NOESY 圖譜54
圖二十五、化合物4 之光譜資料圖56
圖二十六、化合物4 之NOESY 立體圖57
圖二十七、G8-7-6-A (4) 之1H-NMR 圖譜58
圖二十八、G8-7-6-A (4) 之13C-NMR圖譜59
圖二十九、G8-7-6-A (4) 之HMQC 圖譜60
圖三十、G8-7-6-A (4) 之HMBC 圖譜61
圖三十一、G8-7-6-A (4) 之COSY 圖譜62
圖三十二、G8-7-6-A (4) 之NOESY 圖譜63
圖三十三、化合物5 之光譜資料圖65
圖三十四、化合物5 之NOESY 立體圖66
圖三十五、G8-7-5-A (5) 之1H-NMR 圖譜67
圖三十六、G8-7-5-A (5) 之13C-NMR 及DEPT 圖譜68
圖三十七、G8-7-5-A (5) 之HMQC 圖譜69
圖三十八、G8-7-5-A (5) 之HMBC 圖譜70
圖三十九、G8-7-5-A (5) 之COSY 圖譜71
圖四十、G8-7-5-A (5) 之NOESY 圖譜72
圖四十一、化合物1-5 之可能生合成路徑76

表目錄
頁次
表一、G8-7-7-A (1) 之1H-、13C- NMR dataa、HMBC及
COSY 關連14
表二、G8-9-15-30-A (2) 之1H-、13C- NMR dataa、HMBC
及COSY 關連16
表三、G8-10-B (3) 之1H-、13C -NMR dataa、HMBC及
COSY 關連18
表四、G8-7-6-A (4) 之1H-、13C -NMR dataa 、HMBC及
COSY關連20
表五、G8-7-5-A (5) 之1H-、13C- NMR dataa、HMBC及
COSY 關連22
表六、G8-7-7-A (1)、G8-9-15-30-A (2) 及cespitulactone A
(33) 之1H-、13C- NMR 數值比較a 44
表七、G8-10-B (3)、G8-7-6-A (4) 及G8-7-5-A (5)
之1H-、13C- NMR數值比較a 73
1. Wani, M.C.; Taylor, H.L.; Wall, M.E.; Coggon, P.; McPhail, A.
“ Plant Antitumor Agents. VI. The Isolation and Structure of Taxol, a
Novel Antileukemic and Antitumor Agent from Taxus breoifolia ” J.
Am. Chem. Soc. 1971, 93, 2325-2327
2. Schiff, P.B.; Fant, J.; Horwitz, S.B. “Promotion of microtubule
assembly in vitro by taxol” Nature, 1979, 277, 665 – 667
3. Wall, M.E.; Wani, M.C.; Cook, C.E.; Palmer, K.H.; McPhail, A.T.;
“Plant Antitumor Agents. I. The Isolation and Structure of
Camptothecin, a Novel Alkaloidal Leukemia and Tumor Inhibitor
from Camptotheca acuminata” J. Am. Chem. Soc. 1966, 30,
3888-3891
4. Hsiang, Y.H.; Hertzberg, R.; Hecht, S.; Liu, L.F.; “Camptothecin
induces protein-linked DNA breaks via mammalian DNA
topoisomerase I” J. Biol. Chem. 1985, 260, 14873-14878,
5. Coval, S. J.; Coross, S.; Bemardinelli, G.; Jefford, C. W. “Brianthein
V, a New Cytotoxic and Antiviral Diterpene Isolated from Briareum
asbestinum” J. Nat. Prod. 1988, 57, 981-984.
6. Bloor, S. J.; Schmitz, F. J.; Hossain, M. B.; Van der Helm, D.
“Diterpenoids from the gorgonian Solenopodium stechei” J. Org.
Chem. 1992, 57, 1205-1216.
7. Schmitz, F. J.; Schuiz, M. M.; Siripitayananon, J.; Hossain, M. B.;
Van der Helm, D. “New Diterpenes from the Gorgonian
Solenopodium excavatum” J. Nat. Prod. 1993, 56, 1339-1349.
8. Pordesimo, E. 0.; Schmitz, F. J.; Ciereszko, L. S.; Hossain, M. B.;
Van der Helm, D. “New briarein diterpenes from the Caribbean
gorgonians Erythropodium caribaeorum and Briareum sp” J. Org,
Chem. 1991, 56, 2344-2357.
9. Shin, J.; Park, M.; Fenical, W. “The junceellolides, new
anti-inflammatory diterpenoids of the briarane class from the chinese
gorgonian junceella fragilis” Tetrahedron 1989, 45, 1633-1638.
10. Dauben, W.G.; Dauben, W.E.; Thiessen, P.; Resnick, R. “Cembrene, a
Fourteen-Membered Ring Diterpene Hydrocarbon, 1, 2” J. Org,
Chem 1965, 30, 1693-1698
11. Dauben, W.G.; Dauben, W.E.; Thiessen, P.; Resnick, R. “Cembrene,
A 14-Membered Ring Diterpene Hydrocarbon” J. Am. Chem. Soc.
1962, 84, 2015 -2016
12. Burks, J. E.; van der Helm, D.; Chang, C. Y.; Ciereszko, L. S.
“Ammonium hexaammine-tri-g-hydroxo-dicobalt tetrachloride,[(NH3)
3Co (OH) 3Co (NH3) 3] 3+. NH. 4Cl” Acta Cryst., 1977, B33, 704.
13. Rodríguez, A. D.; Ramírez, C.; Cóbar, O. M. “Briareins C-L, 10 New
Briarane Diterpenoids from the Common Caribbean Gorgonian
Briareum asbestinum” J. Nat. Prod. 1996, 59, 15.-22
14. Uchio, Y.; Nakatani, M.; Hase, T.; Kodama, M.; Usui, S.; Fukazawa,
Y. “A new eunicellin-based diterpene from an okinawan soft,
Cladiella sp.” Tetrahedron lett. 1989, 30, 3331-3332
15. Bowden, B.F.; Coll, J. C.; Dai M.C. “Studies of Australian Soft
Corals. XLIII. The Structure Elucidation of a New Diterpene From
Alcyonium molle” Aust. J. Chem 1989, 42, 665-673
16. Bai, R.; Pettit, G.R.; Hamel, E. “Dolastatin 10, a powerful cytostatic
peptide derived from a marine animal. Inhibition of tubulin
polymerization mediated through the vinca alkaloid binding domain”
Biochem Pharmacol 1990, 39, 1941-1949
17. Rinehart Jr, K.L.; Gloer, J.B.; Cook Jr, J.C.; Mizsak, S. A.; Scahill
T.A. “Structures of the didemnins, antiviral and cytotoxic
depsipeptides from a Caribbean tunicate” J. Am. Chem. Soc. 1981,
103, 1857-1859
18. Pettit, G.R.; Herald, C.L.; Doubek, D.L.; Herald, D.L.; Arnold, E.;
Clardy, J. “Isolation and structure of bryostatin 1” J. Am. Chem. Soc.
1982, 104, 6846-6848
19. Cheer, C. J.; Smith, D. H.; Djerassi, C.; Tursch, B.; Braekman, J. C.;
Daloze, D. “Applications of Artificial Intelligence for
ChemicalInference-XXI: Chemical Studies of Marine
Invertebrates-XVII. The Computer-Assisted Identification of
[+]-Palustrol in the Marine Organism Cespitularia sp., aff.
subviridis” Tetrahedron 1976, 32, 1807-1810.
20. Braekman, J. C.; Daloze, D.; Ottinger, R.; Tursch, B. “Chemical
Studiesof Marine Intertebrates. XXVII. On the Absolute
Configuration of Aromadendrane Sesquiterpenes from the Soft Coral
Cespitularia aff. Subviridis” Experientia 1977, 33, 993.
21. Bowden, B. F.; Coll, J. C.; Mitchell, S. J.; Stokie, G. J.; Blount, J. F.
“Studies of Australian soft coral. VIII A Chemical and
Crystallographic Study of a Novel Bicyclic Diterpene Alcohol with a
Rearranged Skeleton from an Unknown Species of Soft Coral”Aust. J.
Chem. 1978, 31, 2039-2046.
22. Bowden, B. F.; Braekman, J. C.; Coll, J. C.; Mitchell, S. J. “Studies
of Australian Soft Corals. XX A New Sesquiterpene Furan from Soft
Corals of the Family Xeniidae and an Examination of Clavularia
inflate from North Queensland Waters” Aust J. Chem. 1980, 33,
927-932.
23. Burns, K. P.; Kazlauskas, R.; Murphy, P. T.; Wells, R. J.; schönholzer,
P. “Two Cembrances from Cespitularia Species (Soft Coral)” Aust. J.
Chem.1982, 35, 85-94.
24. Bowden, B. F.; Coll, J. C.; Tapiolas, D. M. “Studies of Australian
Soft Coral. XXX A Novel Trisnorsesquiterpene form a Cespitularia
Species and the Isolation of Guaiazulene from a small Blue
Alcyonium Species” Aust. J. Chem. 1983, 36, 211-214.
25. Askoka, M.; Kosaka, T.; Itahana, H.; Takei, Hi. “Total Synthesis of
Clavukerin A and Its Epimer” Chem. Lett. 1991, 20, 1295-1298.
26. Bowden, B. F.; Coll, J. C.; Gulbis, J. M.; Mackay, M. F.; Willis, R. H.
“Studies of Australian Soft Corals. XXXVIII Structure Determination
of Several Diterpenes Derived from a Cespitularia Species
(Coelenterata, Octocorallia, Xeniidae)” Aust. J. Chem. 1986, 39,
803-812.
27. König, G. M.; Wright, A. D. “A New Caryophyllene-Based Diterpene
from the Soft Coral, Cespitularia sp.” J. Nat. Prod. 1993, 56,
2198-2200.
28. Coll, J. C.; Kearns, P. S.; Rideout, J. A. “Isolation of Novel Diterpene
Triacetate from Two Soft Corals of the Order Alcyonacea” J. Nat.
Prod. 1998, 61, 835-837.
29. Duh, C.-Y.; El-Gamal, A. A. H.; Wang, S.-K.; Dai, C.-F. “Novel
Terpenoids from Formosan Soft Carol Cespitularia Hypotentaculata”
J. Nat. Prod. 2002, 64, 1028-1031.
30. Shen, Y.-C.; Lin, Y.-S.; Kuo, Y.-H.; Cheng, Y.-B. “Cespitulactams A,
B, and C, three new nitrogen-containing diterpenes from Cespitularia
taeniata May”Tetrahedron Letters 2005, 46, 7893–7897.
31. Shen, Y.-C.; Ho, C.-J.; Kuo, Y.-H.; Lin, Y.-S. “Cespitulactones A
and B, new diterpenoids from Cespitularia taeniata” Bioorg. Med.
Chem. Lett. 2006, 16, 2369-2372.
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