Unlike 3wd, 4 exhibits high reactivity at the C3 site, which also renders itself an unstable molecule against chromatography. However, electrophilic substitution can proceed on 4 without purification. For example, reaction between the crude product of 4 and Vilsmeier reagent affords a C3-dimethylaminomethylidene derivative 5. Hydrolysis of 5 in NaOH generates C3-formyl derivative 6. 6 can be deprotonated at the N2 site with NaH and undergo further nucleophilic methylation with CH 3 I to produce 7. Collectively, these transformations have allowed the complete erasure of any trace of original reactivity-assisting groups and installation of structually completely unrelated appendages, thus offering an enabling tool for accessing distinct chemical space. As a second illustrative example, 4 can also undergo initial azo derivatization at the C3 site and subsequent methylation at the N2 site, affording 8 and 9, respectively.