| Abstract: | Herein we report a total synthesis of the indolohydroazocine natural product actinophyllic acid. The target molecule was retrosynthetically deconvoluted to render a greatly simplified and symmetrical [4.4.1] bicyclic trienone, the desymmetrization of which was carefully examined under a variety of conditions, including oxidative, reductive, and transition‐metal‐catalyzed transformations. Ultimately, the successful synthetic strategy featured chemoselective catalytic dihydroxylation, desymmetrizing nitrile oxide dipolar cycloaddition, and palladium‐catalyzed aminoarylation to sequentially modify the three olefins within the trienone, followed by a late‐stage reductive cascade indolization and alkylation to complete the target molecule. |
