Abstract
Heteropolycyclic frameworks are widely represented in biologically and pharmaceutically relevant compounds; however, methods to synthesize these frameworks often result in heterocycles containing predominantly sp2-hybridized carbons. Herein we describe a heteroannulation scheme featuring a double protonation of a tungsten η2-anisole complex. The resulting dicationic intermediate reacts with activated arenes through an electrophilic aromatic substitution reaction to form an oxocarbenium complex, which can be reduced to an allylic ether complex. Subsequent acidolysis results in a π-allyl complex that can react with alcohol or amine substituents of the activated arene reagent to form the desired heteropolycyclic core.