Synthesis of Idarubicinone via Global Functionalization of Tetracene

Herein, we describe the realization of this concept, providing a non-annulative strategy to anthracyclines from a polynuclear arene. Specifically, tetracene was converted to idarubicinone, the aglycone of the FDA approved anthracycline idarubicin, through the judicious orchestration of Co- and Ru-catalyzed arene oxidation and arenophile-mediated dearomative hydroboration. Such a global functionalization strategy, a combination of site-selective arene and dearomative functionalization, provided the key anthracycline framework in five operations and enabled rapid and controlled access to idarubicinone.