A Formal Total Synthesis of Dysidiolide

A formal total synthesis of the natural product dysidiolide is described. Starting from a Diels−Alder reaction between an enoate and a Rawal
diene, the cyclohexenone 4 was synthesized. A subsequent stereospecific methyl cuprate addition established the desired trans configuration
in the cyclohexane 3. Wacker oxidation of the pentenyl side chain to the diketone 17 followed by an intramolecular aldol condensation led to
the bicyclic enone 2, a key intermediate in a recently reported synthesis of dysidiolide.

本研究报道了天然产物二海绵内酯（dysidiolide）的形式全合成路线。以烯酸酯与罗瓦尔二烯（Rawal diene）的狄尔斯-阿尔德（Diels−Alder）反应为起始步骤，成功合成了环己烯酮4。随后通过立体专一性甲基铜酸盐加成反应，在环己烷3中构建了目标反式构型。对戊烯基侧链进行瓦克尔（Wacker）氧化得到二酮17，再经分子内羟醛缩合反应得到双环烯酮2，该化合物为近期报道的dysidiolide合成路线中的关键中间体。