Formal synthesis of (-)-morphine from D-glucal based on the cascade Claisen rearrangement
Formal synthesis of (-)-morphine from D-glucal based on the cascade Claisen rearrangement
复制标题
DOI：
10.1016/j.tetlet.2007.11.037
复制
发表时间：
2008-01-07
影响因子：
1.8
通讯作者：
Chida, Noritaka
中科院分区：
文献类型：
--
作者：
Tanimoto, Hiroki;Saito, Ryosuke;Chida, Noritaka
描述了(-)-吗啡的正式合成。吗啡中的 C 环是利用 Ferrier 碳环化反应从 D-glucal 制备成光学纯形式，并且基于烯丙基邻位二醇衍生物的级联连续克莱森重排，在一步反应中立体选择性地生成 C 环中的邻位三级和四级立构中心。一步形成二苯并呋喃结构后，分子内Friedel-Crafts型反应有效构建了ABCE-菲呋喃骨架。引入甲苯磺酰胺官能团，然后进行还原环化，得到(-)-二氢异可待因，这是(-)-吗啡的已知合成中间体。 (C) 2007 Elsevier Ltd. 保留所有权利。
The formal synthesis of (-)-morphine is described. The C-ring in morphine was prepared in an optically pure form from D-glucal using Ferrier's carbocyclization reaction, and the vicinal tertiary and quaternary stereocenters in the C-ring were stereoselectively generated in a one-step reaction based on the cascade sequential Claisen rearrangement of an allylic vicinal diol derivative. After the one-step formation of the dibenzofuran structure, the intramolecular Friedel-Crafts type reaction effectively constructed the ABCE-phenanthrofuran skeleton. Introduction of a tosylamide function, followed by reductive cyclization furnished (-)-dihydroisocodeine, the known synthetic intermediate for (-)-morphine. (C) 2007 Elsevier Ltd. All rights reserved.