The first total synthesis of (±)-gelsenicine is reported. The synthetic route is highly efficient (13 steps), featuring (1) a pivotal metal-catalyzed isomerization/rearrangement process that forges the central core of the molecule and (2) two facile C–N bond-forming steps that establish the flanking heterocycles.

The asymmetric synthesis of (–)-naltrexone was achieved by a Rh(i)-catalyzed C–H alkenylation and torquoselective electrocyclization cascade and late-stage C–H hydroxylation.