本論文研究之主要目的在於研究分析兩種柳珊瑚Briareum excavatum(Nutting)及Junceella fragilis(Ridley)的乙酸乙酯萃取物中所含的化學組合成分，並檢測所得到化合物可能具有的細胞毒殺活性。在研究期間共從B. excavatum中分離出十八個新化合物，分別為excavatolides D (1), F-K (2-7),M (8),U-Y (9-13);briaexcavatolides D (14), K (15), L (16), O (17), P (18) 及六個已知化合物excavatolides B (19), C (20), E (21); briaexcavatolides B (22), C (23)及(1S*,2S*,5Z,7S*,8S*,9S*,10S*,11R*,12R*,13Z,17R*)-2,12-diacetoxy-8,17-repoxy-9-hydroxy briara-5,13-dien-18-one (24)。從J. fragilis中共分離出junceellolides E (25), F (26)　兩個新化合物及一個已知化合物 umbraculolide A (27)。化合物1-27均是屬於briarane形式的化合物。

上述所有化合物的結構均是經由物理資料(熔點、旋光點)的測定及各類型的圖譜解析，再配合部分的衍生物製備及相關文獻資料的比對之後而建立。此外，化合物1,9,15,17,18及25等六個化合物的結構及相對立體構型更經由X-ray的單晶繞射解析做了進一步的證明。另外，化合物２結構中所具有的S-trans diene system; 化合物13在C-4β位置上具有的propionyloxy group;化合物15,16及C-8β及c-17α位置上的hydroxy groups;化合物17,18在C-2β,C-3β及C-4α位置上具有的獨立取代官能基，以及化合物25,26中以船型結構(boat conformation)形式存在的six-membered ring，這些較為特殊的分子構型均是在briarane類的化合物中首次被發現的。

在細胞毒殺活性試驗方面，化合物1,6-8,10,16,18,20-22及24對P-388老鼠血癌細胞具有細胞毒殺活性;化合物7,8,20-22及24對KB人體鼻咽癌細胞具有細胞毒殺活性;化合物7,8,20及21對A549人體肺癌細胞具有細胞毒殺活性;化合物1,7,8,18,20及21對HT-29人體腸癌細胞具有細胞毒殺活性。

In our continuing research on the cytotoxic constituents of Taiwanese gorgonian corals, the EtOAc extracts of Briareum excavatum (Nutting) and Junceella fragilis (Ridley) were investigated, repectively. Twenty-four compounds, excavatolides D (1), F-K (2-7), M (8), U-Y (9-13);briaexcavatolides D (14), K (15), L (16), O(17), P (18); excavatolides B (19), C (20), E (21); briaexcavatolides B (22), C (23), and (1S*,2S*,5Z,7S*,8S*,9S*,10S*11R*,12R*,13Z,17R*)-2,12-diacetoxy-8,17-epoxy-9 hydroxy briara-5,13-dien-18-one (24) were isolated from B. excavatum. Three compounds, junceellolides E (25), F (26), and umbraculolide A (27) were isolated from J. fragilis. Among them, compounds 1-18, 25, and 26 are new products. All metabolites 1-27 are briarane-type compounds.

The structures of metabolites 1-27 were determined by physical (mp, optical rotation) and spectral (UV, IR, MS, HRMS, 1D, and 2D NMR) data analyses and chemical methods and by comparison with the related physical and spectral data from other known briarane-type compounds. The structures, including the relative configurations of metabolites 1, 9, 15, 17, 18 and 25 were further confirmed by X-ray single-crystal analyses. Furthermore, the S-trans diene system in 1; the propionyloxy group at the C-4β position of 13; the hydroxy groups at the C-8βand C-17αpositions of 15 and 16; the independent functional groups at the C-2β,C-3β and C-4α positions of 17 and 18, and the boat conformation in the six-membered ring of 25 and 26, all are the first observations in the briarane-type natural products.

The cytotoxicity of the isolates against the P-388(mouse lymphocytic leukemia), KB (hum nasopharyngeal carcinoma), A549 (human lung adenocarcinoma), and HT-29 (human colon carcinoma) cancer cell lines were studied. In the cytotoxicity testing, 1, 6-8, 10, 16, 18, 20-22, and 24 show significant cytotoxicity against the grouth of P-388 cells; 7, 8, 20-22, and 24 show significant cytotoxicity toward KB cells; 7, 8, 20, and 21 show significant cytotoxicity toward A549 cells; 1, 7, 8, 18, 20, and 21 show significant cytotoxicity toward HT-29 cells.

目錄 I
圖目錄 III
表目錄 VIII
中文摘要 1
英文摘要 3

第一章、緒論 7
第一節 研究之重要性及目的 7
第二節 相關文獻回顧 12
第三節 物種形態及分類地位 41
1-3-1 Briareum excavatum的分類地位 42
1-3-2 Junceella fragilis的分類地位 43

第二章、結果與討論 45
第一節　Briareum excavatum的成分研究 45
2-1-1 Excavatolide D (1) 之結構解析 47
2-1-2 Excavatolide F (2) 之結構解析 55
2-1-3 Excavatolide G (3) 之結構解析 62
2-1-4 Excavatolide H (4) 之結構解析 68
2-1-5 Excavatolide I (5) 之結構解析 73
2-1-6 Excavatolide J (6) 之結構解析 78
2-1-7 Excavatolide K (7) 之結構解析 83
2-1-8 Excavatolide M (8) 之結構解析 88
2-1-9 Excavatolide U (9) 之結構解析 95
2-1-10 Excavatolide V (10) 之結構解析 101
2-1-11 Excavatolide W (11) 之結構解析 106
2-1-12 Excavatolide X (12) 之結構解析 111
2-1-13 Excavatolide Y (13) 之結構解析 118
2-1-14 Briaexcavatolide D (14) 之結構解析 124
2-1-15 Briaexcavatolide K (15) 之結構解析 129
2-1-16 Briaexcavatolide L (16) 之結構解析 137
2-1-17 Briaexcavatolide O (17) 之結構解析 143
2-1-18 Briaexcavatolide P (18) 之結構解析 152
2-1-19 Excavatolide B (19) 之結構解析 161
2-1-20 Excavatolide C (20) 之結構解析 163
2-1-21 Excavatolide E (21) 之結構解析 165
2-1-22 Briaexcavatolide B (22) 之結構解析 167
2-1-23 Briaexcavatolide C (23) 之結構解析 169
2-1-24 (1S*,2S*,5Z,7S*,8S*,9S*,10S*,11R*.
12R*,13Z,17R*)-2,12-diacetoxy-8,17
-epoxy-9-hydroxybriara-5,13-dien-18
-one(24) 之結構解析 171
第二節 Junceella fragilis的成分研究 173
2-2-1 Junceellaoide E (25) 之結構解析 173
2-2-2 Junceellaoide F (26) 之結構解析 182
2-2-3 Umbraculolide A (27) 之結構解析 189
第三節　細胞毒殺活性試驗 190
2-3-1 Briareum excavatum部份 191
2-3-2 Junceela fragilis部份 197

第三章 結論 199

第四章 實驗程序 205
第一節 主要設備儀器及材料 205
第二節 樣品之採樣及萃取分離 206
4-2-1 Briareum excavatum部份 206
4-2-1 Junceella fragilis部份 208
第三節 化學反應步驟 209
第四節 細胞毒殺活性篩檢 212
第五節 各化合物之物理及圖譜數據 214

第五章 參考文獻 226

附錄一 個人資料暨研究成果目錄 244
附錄二 Excavatolides D (1) 之X-ray解析數據 250
附錄三 Briaexcavatolide O (17) 之X-ray解析數據 275
附錄四 Briaexcavatolide P (18) 之X-ray解析數據 291

授權書 313

詳參考論文全文資料