The syntheses are summarized in Figure . Coupling dibromide 1 and 1,2-diaminobenzene in DMF at high temperatures (120 • C) led to the formation of an unintended compound 7 similar to the intended diamine 8, but with both nitrogen atoms bound in azepine rings (see Figures in the Supplementary Information). Crystals suitable for X-ray diffractometry allowed for the measurement of the 3D structure (Figure ). By lowering the reaction temperature to 50 • C, we were able to obtain 8 selectively in 91% optimized yield as a central precursor (Figure ; see Figures in the Supplementary Information). In an earlier study, we attempted to synthesize the phenol equivalent amine 8 from dibromide 1 and 2-aminophenol, but found that this compound is sensitive to air and decays quickly to a dihydrooxazole by forming a C-O bond oxidatively . In contrast, we found that amine 8 was stable in open air; no formation of dihydroimidazole side product was observed. Due to its straightforward synthesis, precursor 8 lends itself to further experimentation by allowing a large number of possible scaffolds and functional groups to be coupled to its terminal amine.