Enantioselective Biomimetic Total Syntheses of Kuwanons I and J and Brosimones A and B

Abstract The first enantioselective total syntheses of prenylflavonoid Diels–Alder natural products (−)‐kuwanon I, (+)‐kuwanon J, (−)‐brosimone A, and (−)‐brosimone B have been accomplished from a common intermediate based on a concise synthetic strategy. Key elements of the synthesis include a biosynthesis‐inspired asymmetric Diels–Alder cycloaddition mediated by a chiral ligand/boron Lewis acid, as well as a process involving regioselective Schenck ene reaction, reduction, and dehydration to realize a biomimetic dehydrogenation for generation of the required diene precursor. Furthermore, a remarkable tandem inter‐/intramolecular asymmetric Diels–Alder cycloaddition process was applied for the synthesis of (−)‐brosimone A.