Synthetic studies of natural products with a quaternary stereocenter attahced to nitrogen

氰酸烯丙酯的Sigmatrotic重排提供了一种以高立体专一性的方式将烯丙醇高效转化为烯丙基胺的方法。我们计划将这种重排应用于天然产物的合成。合成工作的重点是合成海洋天然产物，如香叶酰芳丙基异氰酸酯和芒果苷。因此，以乳酸甲酯为起始原料，利用氰酸烯丙酯的S型重排反应，首次实现了香叶基芳醛异氰酸酯的非外消旋合成。发展了一种高效的立体选择性构建不对称四碳立体中心的合成方法，该中心以BOC保护的烯丙基胺的形式含氮化合物。该方法被用于合成海洋生物碱、芒果苷A和C。

Sigmatropic rearrangement of allyl cyanate offers an effcient transformation of the allyl alcohols into the allyl amines with high stereospecific manner. We have planned to apply this rearrangement to the synthesis of natural products. Synthetic efforts focused on the synthesis of marine natural products, such as geranyllinaloisocyanide and manzacidins. As a result, the first non-racemic synthesis of geranyllinaloisocyanide, starting with lactic acid methyl ester, has been accomplished by exploiting a sigmatropic rearrangement of allyl cyanate. An efficient synthetic method for stereoselective construction of asymmetric quaternary carbon stereocenters, bearing nitrogen in the form of Boc-protected allyl amines, has been developed. This methodology is employed in the synthesis of marine alkaloids, manzacidin A and C.