通过利用C(2) - 对称性破缺策略和史密斯 - 蒂茨偶联反应来控制苔藓抑素B环中的烯烃几何结构。

Control of olefin geometry in the bryostatin B-ring through exploitation of a C(2)-symmetry breaking tactic and a Smith-Tietze coupling reaction.

作者信息

Hale K J, Hummersone M G, Bhatia G S

机构信息

The Christopher Ingold Laboratories, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.

出版信息

Org Lett. 2000 Jul 27;2(15):2189-92. doi: 10.1021/ol005850y.

DOI:10.1021/ol005850y

PMID:10930240

Abstract

A completely stereocontrolled asymmetric synthesis of an advanced B-ring synthon for the bryostatin family of antitumor agents is reported. Noteworthy features of our synthesis include the Smith-Tietze bis-alkylation reaction between 12 and 13 en route to C(2)-symmetrical ketone 10 and the totally stereoselective conversion of 10 into triol 18 via a Grignard addition tactic. Triol 18 was converted to epoxide 3 in nine steps, and an acid-catalyzed intramolecular Williamson etherification reaction completed the synthesis of 2.

摘要

报道了一种用于抗肿瘤药物苔藓抑素家族的高级B环合成子的完全立体控制的不对称合成方法。我们合成方法的显著特点包括在合成C(2)对称酮10的过程中，12和13之间的Smith-Tietze双烷基化反应，以及通过格氏加成策略将10完全立体选择性地转化为三醇18。三醇18经九步反应转化为环氧化合物3，然后通过酸催化的分子内威廉姆森醚化反应完成了2的合成。