通过无环三取代烯烃的高度对映选择性和非对映选择性亲核环氧化反应实现（-）-plicatic酸的不对称全合成。
Asymmetric total synthesis of (-)-plicatic acid via a highly enantioselective and diastereoselective nucleophilic epoxidation of acyclic trisubstitued olefins.
作者信息
Sun Bing-Feng, Hong Ran, Kang Yan-Biao, Deng Li
机构信息
Department of Chemistry, Brandeis University, 415 South Street, Waltham, Massachusetts 02454-9110, USA.
出版信息
J Am Chem Soc. 2009 Aug 5;131(30):10384-5. doi: 10.1021/ja9039407.
Abstract
The first total synthesis of (-)-plicatic acid has been achieved by a concise and enantioselective route. In this synthesis, a conceptually new strategy featuring an asymmetric epoxidation-intramolecular epoxy-ring-opening Friedel-Crafts reaction sequence was developed for the stereoselective construction of the 2,7'-cyclolignane skeleton bearing contiguous quaternary-quaternary-tertiary stereocenters. The implementation of this strategy was enabled by the development of a modified protocol for the Seebach epoxidation with TADOOH, which affords an unprecedented, highly enantioselective and diastereoselective epoxidation with a range of alpha-carbonyl-beta-substituted acrylates 3.
摘要
通过一条简洁且对映选择性的路线首次实现了（-）-plicatic酸的全合成。在该合成中，开发了一种概念上新的策略，其特征为不对称环氧化-分子内环氧开环傅克反应序列，用于立体选择性构建具有相邻季碳-季碳-叔碳立体中心的2,7'-环木脂素骨架。该策略的实施得益于开发了一种用TADOOH进行Seebach环氧化的改进方案，该方案能与一系列α-羰基-β-取代丙烯酸酯3进行前所未有的、高度对映选择性和非对映选择性环氧化。
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Asymmetric total synthesis of (-)-plicatic acid via a highly enantioselective and diastereoselective nucleophilic epoxidation of acyclic trisubstitued olefins.通过无环三取代烯烃的高度对映选择性和非对映选择性亲核环氧化反应实现（-）-plicatic酸的不对称全合成。
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