Asymmetric Total Synthesis of (-)-Spirochensilide A.

An asymmetric total synthesis of (-)-spirochensilide A has been achieved for the first time. The synthesis features a semipinacol rearrangement reaction to stereoselectively construct the two-vicinal quaternary chiral centers at C8 and C10, a tungsten-mediated cyclopropene-based Pauson-Khand reaction to install the C13 quaternary chiral center, and a furan-based oxidative cyclization to stereoselectively form the spiroketal motif.