Centre de Recherche CNRS de Gif-sur-Yvette, Institut de Chimie des Substances Naturelles, Avenue de la Terrasse, 91198 Gif-sur-Yvette, France.
Org Lett. 2010 Feb 19;12(4):744-7. doi: 10.1021/ol902829e.
The first total synthesis of the naturally occurring enantiomer of exiguolide ((-)-1) has been completed. This very convergent synthesis features the following as main steps: (i) a Trost's ruthenium-catalyzed ene-yne cross-coupling reaction (this complex transformation allows the challenging control of the C5-C28 double bond geometry along with the stereoselective construction of the tetrahydropyran ring A) and (ii) a very efficient one-pot, two-step stereoselective conjugated allylic alcohol substitution that allowed the control of the C15 stereogenic center.
天然对映异构体（-）-1 的外异钩藤内酯的首次全合成已经完成。这种非常收敛的合成具有以下主要步骤：（i）Trost 的钌催化烯炔交叉偶联反应（这种复杂的转化允许对 C5-C28 双键几何形状进行挑战性的控制，同时立体选择性地构建四氢吡喃环 A）和（ii）非常有效的一锅两步立体选择性共轭烯丙醇取代，允许控制 C15 立体中心。
