烯丙基叠氮重排-分子内施密特反应在扭曲型酰胺和生物碱205B、261C全合成中的应用

作为施密特反应的一个重要拓展，烯丙基叠氮重排-分子内施密特反应是烯丙基叠氮混合物中的两个异构体来发生施密特反应，利用中间体能量的差异可以选择性的得到一个C4双键取代的二环内酰胺，此反应非常好的解决了施密特反应在合成C4取代产物时存在的缺陷。本项目书主要是研究此反应在扭曲型酰胺和生物碱205B、261C全合成中的应用。第一部分是利用烯丙基叠氮重排-分子内施密特反应来制备新型的扭曲型酰胺，研究此扭曲型酰胺的物理性质和波谱特征，以及它在有机合成反应中的应用，如亲核取代反应、[2,3]和[3,3]重排反应、付克反应、Tsuji-Trost反应等，为它在医药行业和材料等领域的应用作准备。第二部分是充分利用烯丙基叠氮重排-分子内施密特反应产物中酰胺的特点，先完成一步邻位烷基化和酰胺的还原烷基化，再和双键发生关环反应，最后完成生物碱205B的全合成，并在此基础上，探索生物碱261C的全合成路线。

As an important expansion of Schmidt reaction, allylic azide rearrangement-intramolecular Schmidt reaction is that two isomers of allylic azide mixture can proceed in the Schmidt reaction to selectively afford one C4-vinyl-substituted bicyclic lactam via the energy difference of two intermediates; and then it solved the trouble of Schmidt reaction to synthesize C4-derivatized products. This application is focused on the application of this reaction on the twisted amide and total syntheses of alkaloids 205B and 261C. The first part of this application is to utilize this reaction to prepare novel twisted amides, study the physical and spectral properties of these amides, and find new applications of them in the organic reactions such as nucleophilic displacement, [2,3] and [3,3] rearrangement, Friedel-Crafts reaction, Tsuji-Trost reaction, mainly for industrial application in the pharmaceutics and material fields. The second part of this application is to make full use of amide functionality in the product of allylic azide rearrangement-Schmidt reaction (first alpha-alkylation and reductive alkylation), then make the ring-closure with double bond, finally accomplish the total syntheses of alkaloids 205B, and study the total synthesis of 261C.