In Figure , we applied a series of azine building block-type compounds to the one-pot halogenation reaction, and we selected iodination for most substrates because of its convenient room temperature C-I bond-forming step. Using conditions B-I, the process tolerates pyridines with aryl, alkyl, and acetal substituents at the 2-position . We found that conditions C-I were effective for 3-substituted pyridines 17-20. The one-pot iodination yield of 3-fluoropyridine was low, and we reverted to a two-step process, and isolated the intermediate Zincke imine; we recommend this alternative protocol to obtain higher overall yields of halogenated pyridines in these instances. Pyridines with benzyl, cyano, and ketone substituents at the 4-position are also effective substrates . We then halogenated a series of 2,3-, 2,4-, and 2,5-disubstituted pyridines . Pyridine 26 is notable because of the sensitive 2-chloro substituent; in this case, ring-opening with dibenzylamine was unsuccessful but did occur using N-benzylaniline. Halopyridines 31-33 show that the Zincke imine intermediate overrides the ortho-, para-directing benzyloxy group and maintains 3-selectivity. We formed a set of di-and trihalogenated pyridines from 3,4-disubstituted systems (34-36), and 37-39 are preliminary examples showing this process can halogenate pyrimidines. When using 5-nitroisoquinoline as a substrate, we did not observe ring-opening but instead isolated a dearomatized adduct where dibenzylamine adds to the C1-atom of the NTf-isoquinolinium salt. Subjecting this intermediate to condition B-Br resulted in 4brominated product 40. We observed a similar intermediate in the one-pot process using 5azaindole, resulting in bromide 41. A C6-brominated product 42 formed from 4-ethoxyquinoline; it is less clear what intermediate species operates in this case due to broadening in the 1 H NMR spectra after conditions A. Figure shows proposed halogenation mechanisms and spectroscopic evidence of the dearomatized adducts.