The one-pot synthesis of 3-isopropyl-6-methyl-1H-benzo[f]indole-4,9-dione (3e), N-(4-[isopentylamino]-3,6-dioxocyclohexa-1,4-dien-1-yl)acetamide (4d), 2-(isopentylamino)-6-methylnaphthalene-1,4-dione (5b), and 2-(4-acetamido-3,6-dioxocyclohexa-1,4-dien-1-yl)-N,N-diisopentyl-3-methylbutanamide (6a) has been achieved via either pyrrol/aryl ring formations or amination reactions from the Pd(II)-catalyzed reaction of N-(3,6-dioxocyclohexa-1,4-dien-1-yl)acetamide (2a_BQ) and in the presence of triisopentylamine. More 3-, 4-, 5-, and 6-like derivatives were obtained while other trialkylamines were used. Crystal structures of 3d_O, 3e, 4b, 4c, 4d, 5b, and 6a were determined by single-crystal X-ray diffraction methods. The 3-and 5-like products reveal the formations of newly generated benzene rings with/without substitutions. The formation of 6a also implies an unusual reaction pathway of its generation. Based on the structural conformations of various 3-like products, as well as 6a, mechanisms were proposed to account for the formations of these compounds. Various fascinating conformations of products observed in this work demonstrate the diversities of this type of reactions.