布瑞他汀的全合成：两种环扩布瑞他汀类似物的合成和新一代 C7-C27 片段合成策略的发展。
Total syntheses of bryostatins: synthesis of two ring-expanded bryostatin analogues and the development of a new-generation strategy to access the C7-C27 fragment.
机构信息
Department of Chemistry, Stanford University, Stanford, CA 94305, USA.
出版信息
Chemistry. 2011 Aug 22;17(35):9789-805. doi: 10.1002/chem.201002932. Epub 2011 Jul 21.
Abstract
Herein, we report the synthesis of novel ring-expanded bryostatin analogues. By carefully modifying the substrate, a selective and high-yielding Ru-catalyzed tandem enyne coupling/Michael addition was employed to construct the northern fragment. Ring-closing metathesis was utilized to form the 31-membered ring macrocycle of the analogue. These ring-expanded bryostatin analogues possess anticancer activity against several cancer cell lines. Given the difficulty in forming the C16-C17 olefin at a late stage, we also describe our development of a new-generation strategy to access the C7-C27 fragment, containing both the ring B and C subunits.
摘要
在此，我们报告了新型扩环海鞘素类似物的合成。通过仔细修饰底物，我们采用了选择性和高产率的 Ru 催化串联烯炔偶联/Michael 加成来构建北片段。通过闭环复分解反应形成类似物的 31 元环大环。这些扩环海鞘素类似物对几种癌细胞系具有抗癌活性。鉴于在后期形成 C16-C17 双键存在困难，我们还描述了一种新一代策略的开发，以获得包含环 B 和 C 亚基的 C7-C27 片段。
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