Department of Organic Chemistry, University of Granada, Faculty of Sciences, Spain.
Chemistry. 2012 Oct 1;18(40):12825-33. doi: 10.1002/chem.201201534. Epub 2012 Aug 24.
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 α,β-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.
本文提出了一种基于两个关键的二茂钛(III)介导反应的直接合成多羟基萜类化合物的方法：“头到尾”的巴比尔型烯丙基氯与α,β-不饱和醛的加成反应，该反应可以在非环前体的理想位置引入羟基，随后进行生物启发的自由基环化反应。该方法还用于五环酯肽 1 和 Aspergilloxide 的 C-D 环模型化合物的首次全合成。
