The first asymmetric total synthesis of a structurally unique alkaloid, chamobtusin A (1), is described. The route features a novel aziridine formation from the 1,2-oxazine derivative and a palladium-mediated annulation of the vinylaziridine intermediate.

The total synthesis of chamobtusin A, the first diterpenoid alkaloid isolated from the whole Pinales, is described. Key features of the synthesis include a stereoselective intramolecular Michael addition to install a key stereocenter and an oxidative manipulation to prepare a 2H-pyrrole ring.

Progress toward the total synthesis of hederacines A and B is described. Our approach involves an allylic cyanate-to-isocyanate rearrangement, eneyne ring-closing metathesis, and a transannular reaction between the C-5 amino group and the C-12 position of the perhydroazuleno[5,6-b]furanone intermediate.

Racemic syntheses of 9-epi-hederacine A and 9-epi-hederacine B have been achieved. Key transformations include a transannular hemiaminal formation for construction of the azabicyclo[3.2.1]octane core fused to a cyclopentane ring.

The total synthesis of chamobtusin A, the first diterpenoid alkaloid isolated from the whole Pinales, is described. Key features of the synthesis include a stereoselective intramolecular Michael addition to install a key stereocenter and an oxidative manipulation to prepare a 2H-pyrrole ring.