Convergent Total Synthesis of Aleutianamine

Herein, we describe a convergent total synthesis of the
pyrroloiminoquinone
natural product aleutianamine that exemplifies a novel paradigm for
pyrroloiminoquinone synthesis by hinging upon a convergent intermolecular
carbon–carbon bond forming event. Specifically, the coupling
of a pyrroloquinone monoketal and a siloxythiophene fragment, each
prepared in seven steps from commercially available materials, allows
for access to the entire carbon framework of aleutianamine in only
eight steps. A variety of intriguing skeletal rearrangements, minimal
late-stage redox adjustments, and a carefully choreographed sequence
of carbon–nitrogen bond formations then deliver the natural
product.