HFIP‐Promoted Short Total Synthesis of Gochnatiolide D and Ainsliadimer A from Dehydrozaluzanin C

The total syntheses of gochnatiolide D and ainsliadimer A were achieved through a streamlined one‐pot sequence starting from their biogenetic precursor dehydrozaluzanin C. These biomimetic, protecting group‐free syntheses involve the elegant orchestration of the highly diastereoselective hetero‐Diels‐Alder reaction of dehydrozaluzanin C, its subsequent hydrolysis to gochnatiolide D and finally an aldol reaction to ainsliadimer A, all harnessed by the hydrogen bond propensity and acidity of hexafluoroisopropanol (HFIP), which was utilized as the reaction solvent.