阿里山五味子與中國五味子果實之降三T類成分研究

Abstract

由台灣產阿里山五味子(Schisandra arisanensis)果實與中國產中國五味子(Schisandra chinensis)果實，經過萃取、分配層析、管柱層析、高效液相層析等分離流程，前者得到二十九個(1-2、16-29、37)降三 類化合物包括kadsuric acid (58)、nigranoic acid (108)，後者得到十三個(13-15、26-28和30-36)降三T類化合物。化合物1-15為新化合物，其中化合物1-12來自前者，而化合物13-15由後者分離純化得到。 依照化合物結構中碳的連結和重排的情形，可將這些降三T類化合物區分為schisanartane (C1；12-13、22-30)、18-norschiartane (C3；14、31-34)、18(13-->14)-abeo-schiartane (C4；35、36)、pre-schisanartane (C5；1-4、16-19)、wuweiziartane (C6；5、20)、arisanartane (C10；15、37)、schicagenin (C12；6-7、21)、16,17-seco-preschisanartane (C13；8)、schisarisanartane (C14)、schisarinin (C18)等結構類型，其中化合物9和10屬於同一新穎骨架類型schisarisanartane (C14)之立體異構物，將之命名為schisarisanlactones A和B；此外化合物11為一個具有2-oxa-bicyclo[2.2.1]heptane系統的schisarinin (C18)新骨架化合物，依生合成推測其衍生自C14類型骨架並命名為schisarinin A。 這些化合物的結構均依據一維核磁共振光譜(1H, 13C, DEPT-135和DEPT-90)以及二維核磁共振光譜(COSY, HSQC, HMBC和NOESY)資料而建立，並輔以紅外線光譜、紫外線光譜、圓二色光譜(CD)、旋光值和高解析電灑式質譜等數據。本文亦推導其可能的生合成路徑，並進行試管內之抗HIV-1 proteinase活性測試。

In our investigations of schinortriterpenoids, 29 compounds (1-12, 16-29, 37, 58 and 108) containing 12 new ones (1-12) were isolated from the fruits of Schisandria arisanensis and 13 compounds (13-15, 26-28 and 30-36) containing 3 new ones (13-15) were obtained from the fruits of S. chinensis. They were separated and purified by means of extraction, partition, and extensive column chromatography including HPLC. These nortriterpenoids were further classified into ten skeletons according to the different carbon connections and rearrangement patterns as the schisanartane (C1; 12-13, 22-30), 18-norschiartane (C3; 14, 31-34), 18(13-->14)-abeo-schiartane (C4; 35, 36), pre-schisanartane (C5; 1-4, 16-19), wuweiziartane (C6; 5, 20), arisanartane (C10; 15, 37), schicagenin (C12; 6-7, 21), 16,17-seco-preschisanartane (C13; 8), C14 and C18. Schisarisanlactones A (9) and B (10) are a pair of epimer belonging to a novel skeleton-type of schisarisanartane (C14). It is noteful that compound 11 is an unprecedented nortriterpenoid designated schisarinin A, which possesses a novel framework with 2-oxa-bicyclo[2.2.1]heptane system (C18). All the structures were determined by application of 1D NMR (1H, 13C, DEPT-135 and DEPT-90) and 2D NMR (COSY, HSQC, HMBC and NOESY) spectroscopic analysis, plus the interpretation of IR, UV, CD, optical rotation, and HRESIMS. The plausible biosynthetic pathways for these derivatives were also proposed. The isolated compounds were tested in vitro the inhibition of HIV-1 protease activities. As a result, some compounds exhibited moderate anti-HIV-1 protease activities at the concentration of 10 microM with different cell survival rate.