A Concise Total Synthesis of (+)‐Waihoensene Guided by Quaternary Center Analysis

The four contiguous all‐carbon quaternary centers of waihoensene, coupled with the absence of any traditional reactive functional groups other than a single alkene, render it a particularly challenging synthetic target among angular triquinane natural products. Here, we show that its polycyclic frame can be assembled concisely by using a strategically chosen quaternary center to guide the formation of the other three through judiciously selected C−C bond formation reactions. Those events, which included a unique Conia‐ene cyclization and a challenging Pauson–Khand reaction, afforded a 17‐step synthesis of the molecule in enantioenriched form.