Biomimetic Total Syntheses of Amorfrutins A, B, ( <i>S</i> )‐D and ( <i>R</i> )‐D and Formal Synthesis of Amorfrutin C

Bibenzyl natural products, such as the amorfrutins, contain a heavily substituted aromatic core and display diverse range of biological activities (anti-tumor, anti-diabetic, antimicrobial, antibiotic). In this study, we report unified syntheses amorfrutin A to D either through total or formal synthesis by employing dual biomimetic strategy polyketide aromatization followed remote terpene functionalization. The key structures were synthesized from β-keto dioxinone esters magnesium(II) mediated regioselective C-acylation, palladium catalyzed decarboxylative allylic rearrangement, dehydrative cyclization.