Combining the Power of TiIII-Mediated Processes for Easy Access to Hydroxylated Polycyclic Terpenoids: Synthesis of Sesterstatin 1 and C-D Rings of Aspergilloxide
Combining the Power of TiIII-Mediated Processes for Easy Access to Hydroxylated Polycyclic Terpenoids: Synthesis of Sesterstatin 1 and C-D Rings of Aspergilloxide
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DOI：
10.1002/chem.201201534
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发表时间：
2012-10-01
影响因子：
4.3
通讯作者：
Cuerva, Juan M.
中科院分区：
文献类型：
--
作者：
Jimenez, Tania;Morcillo, Sara P.;Cuerva, Juan M.
提出了一种基于二茂钛(III)介导的关键反应的多羟基萜类化合物的直接获取方法：异戊烯基氯与α,β-不饱和醛的“头对尾”Barbier型加成，这允许在无环前体的所需位置引入羟基，以及随后的仿生自由基环化。该方法也已用于五环司斯特他汀 1 和曲霉氧化物 C-D 环模型化合物的首次全合成。
A straightforward access to polyhydroxylated terpenoids based on two key titanocene(III)-mediated reactions is presented: the "head-to-tail" Barbier-type addition of prenyl chlorides to alpha,beta-unsaturated aldehydes, which allows the introduction of hydroxy groups at desirable positions of the acyclic precursor, and the subsequent bioinspired radical cyclisation. This methodology has been also used in the first total synthesis of pentacyclic sesterstatin 1 and a model compound of the C-D rings of aspergilloxide.