Herein we report the first total synthesis of the indole
diterpenoid
natural product shearilicine by an 11-step sequence via a generalizable
precursor to the highly oxidized subclass of indole diterpenoids.
A native chiral auxiliary strategy was employed to access the target
molecule in an enantiospecific fashion. The formation of the key carbazole
substructure was achieved through a mild intramolecular Heck cyclization,
wherein a computational study revealed noncovalent substrate–ligand
and ligand–ligand interactions that promoted migratory insertion.