Bioorganically Chemical Studies on Antitumor Substances contained in Trees

1.番荔枝内酯类化合物的生物有机化学研究：利用立体选择性反应合成番荔枝内酯类化合物的生物合成中间体Squamostanal-A、epoxyrollin A和diepomuricanin。对合成的epoxyrollin A的光谱分析表明，天然epoxyrollin A的结构是错误的。此外，利用手性嵌段的立体选择性方法合成了番荔枝内酯类化合物（8^2R）和（8^2S）-corossoline以及（+）-4-deoxytecin。从番荔枝科植物紫玉盘（Uvaria purpurea）中分离生物活性成分并进行结构鉴定，以期分离出属于zeylenol的新衍生物.紫杉二萜类化合物的化学转化研究：1）紫杉碱的立体选择性脱乙酰化反应（Mg（OCH_3）_2）和酶法2）2，5，7，9，10，13，20-七乙酰基-3，8-断紫杉-3，8，11-三烯与Pd（Ph_3P）_4在乙酸中反应，得到2，5，10，13，20-五乙酰基-3，8-断序-3，7-二酮-9-酮。3）在Hg（OAc）_2存在下，5-癸氨酰紫杉碱与乙烯基乙醚发生侧链延长反应，得到一个新的含20-甲酰基甲基的紫杉二萜类似物。

1. Bioorganically chemical research on Annonaceous acetogenins : Squamostanal-A, epoxyrollin A and diepomuricanin, which were proposed as biosynthetic intermediates for Annonaceous acetogenins, were synthesized by using stereoselective reactions. The spectral analysis of the synthesized epoxyrollin A showed that the structure proposed for natural epoxyrollin A is mistaken. Furthermore, (8^2R) and (8^2S)-corossoline and (+)-4-deoxygigantecin, Annonaceous acetogenins, were synthesized by the stereoselective methods using chiral bulding blocks. Separation and structural elucidation of biologically active components from Uvaria purpurea, a Chinese plant of Annonaceae species, was tried to separate new derivatives belong to zeylenol.2. Studies on the chemical transformation of taxanediterpenoids.1) Stereoselective deacetylation of taxinine, a major component of Japanese yew, using chemical (Mg(OCH_3)_2 )and enzymatic methods (pancreatine) gave 9,10-deacetyl taxinine.2) Treatment of 2,5,7,9,10,13,20-heptaacetyl 3,8-secotaxa-3,8,11-triene with Pd(Ph_3P)_4 in acetic acid gave 2,5,10, 13,20-pentaacetyl-3,8-secotaxa-3,7-die-9-one. Which was identical with a new minor compound separated from Chinese yew, Taxus mairel.3) Side chain elongation of 5-decinnamoyl taxinine with vinylethylether in the presence of Hg(OAc)_2 gave a new analog of taxanditerpenenoid with 20-formylmethyl group.