Biomimetic total synthesis of the reported structure of (+)-selaginedorffone B

The first enantioselective total synthesis of the reported structure of the structurally unique aromatic tetraterpenoid of anti-cancer potential, (+)-selaginedorffone B (2), has been accomplished from two modified abietane diterpenoids through an intermolecular Diels-Alder reaction between a bio-inspired diene 3 (HOMO counterpart) and dienophile 4 (corresponding LUMO counterpart) in a 23-step sequence, whereas the core framework of the monomeric abietane diterpenoid was constructed via alkyne-activated ene-cyclization. Computational analysis was conducted to reveal the intricate regio and diastereoselectivity of this novel Diels-Alder reaction, strengthening the experimental results. The absolute configuration of the synthesized molecule was validated through X-ray studies of late-stage intermediates as well as comprehensive 2D NMR analysis. The first catalytic enantioselective total synthesis of (+)-selaginedorffone B (2) on a gram scale has been accomplished from two modified abietane diterpenoids, diene 3 and dienophile 4, through a key intermolecular Diels-Alder reaction.