Total synthesis of (-)-tuberostemonine.
Total synthesis of (-)-tuberostemonine.
复制标题
(-)-块百部碱的全合成。
DOI：
10.1021/ja028603t
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发表时间：
2002
影响因子：
15
通讯作者：
Takahashi,Hidenori
中科院分区：
文献类型：
--
作者：
Wipf,Peter;Rector,StaceyR;Takahashi,Hidenori
首次从Cbz-1-酪氨酸经三步反应制得的氢吲哚中间体出发，经24步反应，以1.4%的总收率合成了复杂的五环百部生物碱tuberostemonine。应用了一种创新的合成策略，将氨基酸前体的单个立体中心中继到靶分子的十个立体碳中的九个。合成方法的亮点之一是钌催化剂的三重使用，首先是氮杂环庚三烯闭环复分解，然后是烯烃异构化，然后是交叉复分解丙烯基-乙烯基交换，以及通过使用锂化原酸酯将γ-丁内酯部分立体选择性连接到核心四环素上。
The first total synthesis of the complex pentacyclicStemonaalkaloid tuberostemonine was accomplished in 24 steps and in 1.4% overall yield from a hydroindole intermediate which is readily obtained in three steps from Cbz-l-tyrosine. An innovative synthetic strategy was applied that relays the single stereocenter of the amino acid precursor into nine of the ten stereogenic carbons of the target molecule. Among the highlights of the synthetic methodology are the 3-fold use of ruthenium catalysis, first in an azepine ring-closing metathesis and then in an alkene isomerization followed by a cross-metathesis propenyl−vinyl exchange, as well as the stereoselective attachment of the γ-butyrolactone moiety to the core tetracycle by use of a lithiated ortho ester.