通过 Ireland-Claisen 重排控制环外烯烃的几何形状：巴尔母霉素和利马泽平 E 的立体选择性全合成。

The exocyclic olefin geometry control via Ireland-Claisen rearrangement: stereoselective total syntheses of Barmumycin and Limazepine E.

机构信息

Latvian Institute of Organic Synthesis, Aizkraukles 21, LV-1006, Riga, Latvia.

出版信息

Org Lett. 2013 Sep 6;15(17):4406-9. doi: 10.1021/ol4019453. Epub 2013 Aug 21.

DOI:10.1021/ol4019453

Abstract

Stereoselective total syntheses of Limazepine E and Barmumycin, potent, naturally occurring antitumor agents, are described. The total syntheses control the olefin geometry via a highly selective chelation-controlled Ireland-Claisen rearrangement of a seven-membered lactone-derived boron enolate for the synthesis of (E)-4-ethylidene proline, a crucial building block for a number of natural products.

摘要

立体选择性全合成 Limazepine E 和 Barmumycin，这两种强效的天然抗肿瘤药物，已被描述。全合成通过高度选择性的螯合控制的 Ireland-Claisen 重排来控制烯烃几何形状，该重排涉及一个七元环内酯衍生的硼烯醇，用于合成（E）-4-亚乙基脯氨酸，这是许多天然产物的关键构建块。