A concise total synthesis of (+)-scholarisine A empowered by a unique C-H arylation.

The structurally unique akuammiline alkaloid (+)-scholarisine A was synthesized in 14 steps from a known enone (15 steps from commercial materials) through a route empowered by a unique C-H arylation reaction to forge its polycyclic core. Additional key steps include a pyrone Diels-Alder reaction and a radical cyclization/Keck allylation to fashion the core cage polycycle and one of the molecule's quaternary centers, as well as the use of a carefully positioned pendant hydroxyl group to facilitate the chemoselective reduction of an extremely unreactive lactam in the presence of a readily reduced lactone.