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.