Azatriquinanes. Part 4. The chemistry of azatriquinenamine and its bromination products

Abstract

Azatriquinenamine (5) is the entry point into the azatriquinane heterocycles. Its convex morphology and enamine function involving a bridgehead double bond lead to unusual reactivity. Bromination of 5 gives either a mono- (7) or tetrabromo (8) derivative depending on conditions, the latter of which is highly congested sterically and undergoes unexpected ring opening, rearrangement, and hydrolysis reactions. Careful elimination of HBr from 8 gives a potential precursor (14) to azatriquinene 6, and a dehydrobromination, bromination protocol leads to a potential precursor (18) to azatriquinacene 2.