Synthetic study of hetisine-type aconite alkaloids. Part 1: Preparation of tetracyclic intermediate containing the C14-C20 bond
Synthetic study of hetisine-type aconite alkaloids. Part 1: Preparation of tetracyclic intermediate containing the C14-C20 bond
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DOI：
10.1016/j.tet.2006.04.084
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发表时间：
2006-07-17
期刊：
影响因子：
2.1
通讯作者：
Natsume, Mitsutaka
中科院分区：
文献类型：
--
作者：
Muratake, Hideaki;Natsume, Mitsutaka
（+/-）-乌头生物碱的全合成的全部细节分为三个部分。这里（第1部分），我们描述了关键四环中间体6的制备。我们采用钯催化的分子内α -芳基化反应制备了带角甲酰基的中间体4。然后采用缩醛-烯反应形成C14-C20键，从5得到6。讨论了缩醛反应的反应机理，提出了一种从6中脱除2-羟乙基的方法。(c) 2006 Elsevier Ltd.版权所有。
Full details for the total synthesis of (+/-)-nominine, a hetisine-type aconite alkaloid, are presented in three parts. Here (part 1), we describe the preparation of the key tetracyclic intermediate 6. Our palladium-catalyzed intramolecular alpha-arylation was adopted for preparation of the intermediate 4 with an angular formyl group. An acetal-ene reaction was then employed for C14-C20 bond formation to secure 6 from 5. The reaction mechanism of the acetal-ene reaction is discussed, and a method for removal of the 2-hydroxyethyl group from 6 is developed. (c) 2006 Elsevier Ltd. All rights reserved.