Synthesis of (−)-Mitrephorone A via a Bioinspired Late Stage C–H Oxidation of (−)-Mitrephorone B

We present a bioinspired late-stage C–H oxidation of the ent-trachylobane natural product mitrephorone B to mitrephorone A. The realization of this unprecedented transformation was accomplished by either an iron-catalyzed or electrochemical oxidation and enabled access to the densely substituted oxetane in one step. Formation of mitrephorone C, which is lacking the central oxetane unit but features a keto-function at C2, was not formed under these conditions.