巒大紫珠枝葉之雙萜類成分研究

Abstract

本論文為研究台灣特有種巒大紫珠(Callicarpa randaiensis Hayata)含有之雙萜類成分。其枝葉部位之乙醇萃取物，使用各種管柱層析方法進行分離、純化，並藉由各種光譜分析和文獻查詢鑑定結構，結果共發現十八個化合物，包括十三個新的雙萜類化合物。 新化合物當中，共有六個clerodane type雙萜類callirandainins A-F (1-6)，二個halimane type雙萜類callirandainins G, H (7, 8)，和新穎化合物骨架二種，分別為七/五合環randaininsA, B (9, 10)，以及五/七合環randaininsC, D (11, 12)，推測其生合成路徑是由clerodane/halimane衍生而來。還有abietane type雙萜類新化合物一個callirandainin I (13)。另外，分離出的已知化合物共有五個，3-oxo-17a,20a-cleroda-13(14)-en-15,16-olide (14)、3a,4b-dihydroxy-17a,20a-cleroda-13(14)-en-15,16-olide (15)、3a-hydroxy-17a,20a-cleroda-5(6),13(14)-dien-15,16-olide (16)、dehydroabietic acid (17)和三萜類b-amyrin (18)。 以上化合物的結構主要是利用核磁共振光譜1D NMR(1HNMR、13CNMR)及2D NMR (COSY、HMQC、HMBC、NOESY)解析，加上各種物理數據分析，如旋光度、紅外線吸收光譜、紫外線吸收光譜、圓二色性光譜、高解析電灑式質譜，並利用化學資料庫Reaxys與SciFinder查詢相關文獻輔助鑑定結構。 最後將所分得的化合物進行抗人類癌細胞活性檢測。

This thesis is a chemical investigation of diterpenoid constituents from Callicarpa randaiensis Hayata, an endemic species in Taiwan. The ethanol extracts of the twigs and leaves were separated by extensive column chromatography to give eighteen compounds, including thirteen new diterpenoids. Callirandainins A-F (1-6) are new clerodane diterpenoids while callirandainins G, H (7, 8) belong to halimane scaffold. Interestingly, two novel skeletons of 7/5 and 5/7 ring systems were discovered, namely randainins A-D (9-12). And callirandainin I (13) is a new abietane-type diterpenoid. In addition, five known compounds were also isolated and characterized as3-oxo-17a,20a-cleroda-13(14)-en-15,16-olide (14),3a,4b-dihydroxy-17a,20a-cleroda-13(14)-en-15,16-olide (15),3a-hydroxy-17a,20a-cleroda-5(6),13(14)-dien-15,16-olide (16), dehydroabietic acid (17) and oleane-type triterpenoid b-amyrin (18). The above structures were elucidated on the basis of spectroscopic analysis such as 1D NMR (1H NMR, 13C NMR), 2D NMR (COSY, HMQC, HMBC, NOESY) techniques and physical methods including optical rotation, infrared spectroscopy (IR), ultraviolet spectroscopy (UV), circular dichroism spectroscopy (CD) and high resolution mass spectroscopy (HRMS). Moreover, the data were compared with those of published literatures from the databases Reaxys and SciFinder. Finally, cytotoxic activity was tested and evaluated.