Synthesis and Reactions of Benzannulated Spiroaminals: Tetrahydrospirobiquinolines

An efficient two-step synthesis of symmetrical and unsymmetrical tetrahydrospirobiquinolines from o -azidobenzaldehydes is reported. A novel series of tetrahydrospirobiquinolines was prepared by sequential double-aldol condensation with acetone, cyclopentanone, and cyclohexanone to form the corresponding o , o '-diazido-dibenzylidene-acetone, -cyclopentanone, and -cyclohexanone derivatives, respectively, and hydrogenation-spirocyclization. The spirodiamines were further derivatized by electrophilic aromatic bromination, Suzuki coupling, and N -alkylation, all of which proceeded with preservation of the spirocyclic core.