Development of Novel Organic Fine Chemicals based on Polycycles

在本项目中，为了开发基于金刚烷等多环的新型工业有机精细化学品，我们进行了一些选择性的碳环和杂多环的设计和合成。主要研究结果如下：1)将金刚烷中容易得到的桥亚胺-4-氮杂-高-4-烯转化为相应的N-氧化物，即一种新型的桥式硝酮，该中间体可用于合成异恶唑烷、异恶唑啉、吡咯等稠合杂环化合物。3)一种环核苷，2，2‘-脱氢胸腺嘧啶衍生物被证明是具有重要生物意义的3’-取代阿拉伯核苷的中间体。4)利用过渡金属诱导的偶联反应，合成了一种简单的β-氯-β-三氟甲基Delta^&lt；α，β&gt；-羰基化合物。还开发了一种通过乙酰基吡咯衍生物的[4，2]环加成反应合成吲哚骨架的新方法。这些化合物有望成为生物活性化合物的有用合成块。

In this project, design and synthesis of some selected carbo- and heteropolycycles have been carried out in order to develop novel organic fine chemicals for industrial use based on polycycles like adamantane. The results can be summarized as follows :1) A bridge-imine, 4-azahomoadamant-4-ene obtainable readily from adamantane was converted to the corresponding N-oxide, i.e., a novel bridged nitrone, which was shown to be useful intermediate for synthesis of homoadamantano [4,5] fused heterocycles such as isooxazolidines, isooxazolines, and pyrroles etc.2) A short-step synthesis of quinazoline alkaloids, Rutecarpine and Tryptanthrin has been developed via intramolecular aza-Wittig methodology. A novel route to polyazamacrocycles has been developed via quinazolinone-annelation of lactams, followed by reductive ring-enlargement.3) A cyclonucleoside, 2,2'-anhydrothymine derivative was shown to be useful inter-mediate for biologically important 3'-substituted arabinonucleosides.4) A facile synthesis of beta-chloro-beta-trifluoromethyl DELTA^<alpha,beta>-carbonyl compounds has been developed by using transition metal-induced coupling reaction. Also a novel route to indole skeletons via [4+2] cycloaddition reaction of acetyl pyrrole derivatives has been developed. These compounds are expected as useful synthetic blocks for bioactive compounds.