Total synthesis of alstofonidine via its putative biosynthetic congener

Abstract A first total synthesis of alstofonidine is described from the pentacyclic core, an advanced intermediate reported previously. The pentacyclic core facilitated putative biosynthetic congener access, thereby allowing a rapid synthesis of alstofonidine from the proposed biosynthetic pathway. Besides, the model substrate to obtain a simplified bicyclic acetal portion also leveraged in accomplishing structurally complex alstofonidine effortlessly.