Development of New Methodologies for the efficient synthesis of biologically active compounds

开发有效合成生物活性化合物的新方法

基本信息

批准号：
12660101
负责人：
TANIMORI Shinji
金额：
$ 0.45万
依托单位：
Osaka Prefecture Unicersity
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

项目摘要

1. Development of transition metal-catalyzed tandem organi reactionReaction of 2-butenylene dicarbonate with primary amine was catalyzed by palladium-phosphine catalyst to produce novel 5-vinyl oxazolidone in good yield. Asymmetric induction of this reaction was achieved by using chiral bidentate phosphine ligand to produce chiral oxazolidone derivatives in 90 % enantio selectivity.2. Synthetic approach for both enantiomars of jasmonic acidReaction of meso-1, 4-diacetoxycyclopentene with dimethyl malonate in the presence of palladium-chiral phosphine catalyst possessing C_2-symmetry to give alkylated product in 85 % enentiomeric purity. The product was converted into knouw intermedate for the synthesis of jasmonic acid.3. Synthetic approach for asperparaline, an indolidine alkaloid posessing potent Paralytic activityEnyne derived from praline was subjected to Pauson-Khand cycloaddition using cobalt octacarbonyl to produce tricyclic indolidine, which was treated with methylamine to gibe teracyclic bridged amide, a potential intermediated for asperparaline C in good yield.4 Synthetic approach for cyclic ADP-ribose, a second messenger for Ca^<2+> releaseEfficient chemical synthesis of NMN and derivatives, a precursor of NAD, was developed Reaction of tetraacetate prepared fron D-ribose with nicotinamide in the presence of Lewis acid (TMSOTf) followed by treatment of methanol to provide NAR, which was phopholylated to give desired NMN in good yield.

1. 过渡金属催化串联有机反应的发展在钯-膦催化剂的催化下，2-丁烯基二碳酸酯与伯胺反应制备新型5-乙烯基恶唑烷酮，收率良好。通过使用手性二齿膦配体实现了该反应的不对称诱导，生成手性恶唑烷酮衍生物，对映选择性达到90％。 2．茉莉酸两种对映体的合成方法内消旋1, 4-二乙酰氧基环戊烯与丙二酸二甲酯在具有C_2对称性的钯手性膦催化剂存在下反应，得到对映体纯度为85%的烷基化产物。将产物转化为已知的茉莉酸合成中间体。 3．具有有效麻痹活性的吲哚啉生物碱阿斯帕林的合成方法以果仁糖为原料，使用八羰基钴进行 Pauson-Khand 环加成反应生成三环吲哚啶，再用甲胺处理得到四环桥酰胺，这是一种潜在的阿斯帕林 C 中间体，收率良好.4 环状 ADP-核糖（第二信使）的合成方法Ca^2+释放开发了NMN及其衍生物（NAD前体）的高效化学合成在路易斯酸（TMSOTf）存在下由D-核糖制备的四乙酸酯与烟酰胺反应，然后用甲醇处理以提供NAR，其进行磷酸化，以良好的收率得到所需的 NMN。