Chemical and Biological Studies on Production of Camptothecin-related Molecules by Use of the Domestic Medicinal Resource Plant

[L]茜草科牧草再生植株和毛状根中的次生代谢物(1)牧草再生植株的成分：由愈伤组织培养经分化形成的再生植株，产生喜树碱、5种喜树碱相关生物碱等9种已知化合物。(2)发根植物毛状根成分：生根农杆菌pRi15834；pGSGLucl接种于再生植株，获得毛状根。从固体培养的毛状根中分离得到4个与喜树碱有关的生物碱，包括3(S)-和3(R)-脱氧木霉糖苷和3个蒽醌类化合物。未检测到喜树碱的存在。从液体培养的毛状根中分离得到4种与喜树碱有关的生物碱，包括喜树碱和6种蒽醌类化合物。结果表明，野牡丹的再生植株和毛状根均产生喜树碱。3(S)-和3(R)-脱氧木糖苷在毛状根和野生植物中都存在，这一发现对于阐明喜树碱的生物合成具有重要意义。[2]喜树碱相关化合物的合成研究根据可能的生物发生途径，由3(S)-和3(R)-脱氧木糖苷通过C-7位还原脱氧，合成了3(S)-和3(R)-脱氧木糖苷，并确定了其结构和绝对构型。

[l] Secondary metabolites isolated from regenerated plants and hairy roots of Ophiorrhiza pumila (Rubiaceae)(1) Constituents of regenerated plants of O.pumila : Regenerated plants, which were formed from callus cultures through differentiation, produced camptothecin, five camptothecin-related alkaloids and other nine known compounds. A new gluco camptothecin, 9-beta-D-glucosyloxy-camptothecin, was also isolated.(2) Constituents of hairy roots of O.pumila : Hairy roots of O.pumila were obtained by the inoculation of Agrobacterium rhizogenes (pRi15834 ; pGSGlucl) to regenerated plants. From hairy roots cultivated on the solid medium, four camptothecin-related alkaloids including 3(S)- and 3(R)-deoxypumiloside and three anthraquinones were isolated. The existence of camptothecin could not be detected. From hairy roots cultivated in the liquid medium, four camptothecin-related alkaloids including camptothecin and six anthraquinones were isolated. It was found that both regenerated plants and hairy roots of O.pumila produce camptothecin. The finding that both the 3(S)- and 3(R)-deoxypumiloside are present in hairy roots as in the wild plants is quite important in clarification of the camptothecin biosynthesis.[2] Synthetic studies of camptothecin-related compoundsAccording to the plausible biogenetic pathway, both the 3(S)- and 3(R)-deoxypumiloside were converted from 3(S)- and 3(R)-pumiloside through a reductive deoxygenation at C-7 position in pumiloside.9-beta-D-Glucosyloxycamptothecin, a new alkaloid isolated from regenerated plants of O.pumila, was synthesized and its structure and the absolute configuration were established.