Toumi Mathieu, Couty François, Evano Gwilherm
Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint Quentin en Yvelines, 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
J Org Chem. 2008 Feb 15;73(4):1270-81. doi: 10.1021/jo702092x. Epub 2008 Jan 19.
The total synthesis of (-)-paliurine E is described in 14 steps and 11% overall yield. The first successful application of ene--enamide ring-closing metathesis for macrocyclization serves as the foundation for this synthesis and allowed for a straightforward installation of the challenging cyclic enamide together with the macrocycle. In the course of these synthetic studies, we also found that very subtle and minor structural modification of the enamide resulted in dramatic and unexpected changes of their reactivity since a primary amide or an aromatic aldehyde can be obtained after reaction with Grubbs' second-generation catalyst. Further insights on the macrocyclization by ene--enamide RCM are also discussed.
（-）-帕柳林E的全合成以14步完成，总产率为11%。烯-烯酰胺闭环复分解反应首次成功应用于大环化反应，为该合成奠定了基础，并使得具有挑战性的环状烯酰胺与大环能够直接安装。在这些合成研究过程中，我们还发现，烯酰胺非常细微的结构修饰会导致其反应性发生显著且意想不到的变化，因为与第二代格拉布催化剂反应后可得到伯酰胺或芳香醛。此外，还讨论了烯-烯酰胺RCM大环化反应的更多见解。
