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

氰酸烯丙酯的σ转移重排反应能使烯丙醇高效地转化为烯丙基胺，并具有高度的立体专一性。我们计划将这种重排应用于天然产物的合成。合成工作集中在海洋天然产物的合成上，例如香叶基亚麻酸异氰化物和manzacidins。因此，第一个非外消旋合成香叶基linaloisocyanide，从乳酸甲酯，已完成利用sigmatropic重排的氰酸烯丙酯。本文报道了一种立体选择性地合成叔丁氧羰基保护的烯丙胺类含氮不对称季碳立体中心的方法。该方法用于合成海洋生物碱，manzacidin 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.