Asymmetric Total Synthesis of Hasubanan Alkaloids: Periglaucines A–C, N,O‐Dimethyloxostephine and Oxostephabenine

Abstract We report herein the asymmetric total synthesis of periglaucines A–C, N,O‐dimethyloxostephine and oxostephabenine. The key strategies used include: 1) a RhI‐catalyzed regio‐ and diastereoselective Hayashi‐Miyaura reaction to connect two necessary fragments; 2) an intramolecular photoenolization/Diels–Alder (PEDA) reaction to construct the highly functionalized tricyclic core skeleton bearing a quaternary center; 3) a bio‐inspired intramolecular Michael addition and transannular acetalization to generate the aza[4.4.3]propellane and the tetrahydrofuran ring.