α-环官能化足叶草内酯的简便合成。文替内酯B结构的修正。

A convenient synthesis of a-ring-functionalized podolactones. Revision of the structure of wentilactone B.

作者信息

Barrero Alejandro F, Herrador María M, Quílez del Moral José F, Valdivia Mónica V

机构信息

Department of Organic Chemistry, Institute of Biotechnology, University of Granada, Avda. Fuentenueva, 18071 Granada, Spain.

出版信息

Org Lett. 2002 Apr 18;4(8):1379-82. doi: 10.1021/ol0257070.

DOI:10.1021/ol0257070

PMID:11950367

Abstract

A new route to podolactones functionalized in the A ring has been achieved. Two key steps were employed in this synthesis, the construction of the bicyclic skeleton via a Mn(III)-mediated radical cyclization and the transformation of this bicyclic intermediate into the tetracyclic podolactone skeleton through a Pd (II)-mediated bislactonization of the corresponding conjugate diene. The reported synthesis of 3beta-hydroxy-13,14,15,16-tetranorlabda-7,9(11)-dien-(19,6beta),(12,17)-diolide (1) let us reassign the structure of wentilactone B, for which structure 1 was wrongly reported. [reaction: see text]

摘要

已实现了一种在A环中官能团化的足叶草内酯的新合成路线。该合成采用了两个关键步骤，即通过锰(III)介导的自由基环化构建双环骨架，以及通过钯(II)介导的相应共轭二烯的双内酯化将该双环中间体转化为四环足叶草内酯骨架。所报道的3β-羟基-13,14,15,16-四降-labda-7,9(11)-二烯-(19,6β),(12,17)-二内酯(1)的合成使我们重新确定了文替内酯B的结构，之前其结构被错误报道为1。[反应：见正文]