A synthetic approach for constructing the 3/6/6/5-fused tetracyclic skeleton of tenuipesine A

Abstract

An efficient approach toward the 3/6/6/5-fused tetracyclic skeleton of tenuipesine A has been accomplished. The strategy featured 1) a tandem Mitsunobu and 3,3-rearrangement reaction yielding the key intermediate 7 with two adjacent all-carbon quaternary centers with high d.r.; and 2) a tandem DBDMH-mediated semipinacol rearrangement via a 1,2-oxygen migration of an allylic hemiketal to construct the highly substituted tetrahydropyran ring.

Keywords: Mitsunobu reaction; rearrangement; semipinacol; synthesis; tenuipesine A.