Total synthesis of (+)-suaveolindole: establishment of its absolute configuration.
Total synthesis of (+)-suaveolindole: establishment of its absolute configuration.
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( )-suaveolindole 的全合成：建立其绝对构型。
DOI：
10.1021/ja075100k
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发表时间：
2007
影响因子：
15
通讯作者：
Danishefsky,SamuelJ
中科院分区：
文献类型：
--
作者：
Velthuisen,EmileJ;Danishefsky,SamuelJ
本文介绍了（+）-suaveolindole的两种全合成方法。最初的策略使用6-exo-Heck环化来产生瞬时sp3碳钯酸。该中间体成功地与吲哚3-锡烷偶联以组装天然产物的大部分碳框架。然而，由于本文所述的问题，这种令人感兴趣的路线是不可行的。为了达到我们的目标，从第一个策略中吸取的教训指导我们开发爱尔兰酯烯醇化物重排的显著扩展，其中四取代的异亚丙基和α-处理的羧甲基官能团在单个事件中引入。这一关键反应使得（+）-suaveolindole的首次合成非常简洁。
This communication describes two approaches toward the total synthesis of (+)-suaveolindole. The initial strategy uses a 6-exo-Heck cyclization to generate a transient sp3carbopalladate. This intermediate was successfully coupled with an indole 3-stannane to assemble the majority of the carbon framework of the natural product. However, due to problems described herein, this interesting route was not viable. To reach our target, lessons learned from the first strategy directed us to develop a significant extension of the Ireland ester enolate rearrangement in which the tetra-substituted isopropylidene group and the α-disposed carboxymethyl function are introduced in a single event. This key reaction enables a remarkably concise inaugural synthesis of (+)-suaveolindole.