First total synthesis of rhodexin A.

An efficient total synthesis of rhodexin A (1) is reported. An initial inverse-electron-demand Diels-Alder reaction of the acyldiene 6 with the silyl enol ether 7 gave the cycloadduct 8 with the required 4 contiguous stereocenters in a single step. This compound was then transformed into the tetracyclic enone 16, which was converted to rhodexin A (1).