Comprehensive NMR and Spectroscopic Data

¹H NMR spectra were recorded on a Bruker AV-400 spectrometer in chloroform-d₃. Chemical shifts are reported in ppm with the internal TMS signal at 0.0 ppm as a standard. The data is being reported as (s = singlet, d = doublet, t = triplet, m = multiplet or unresolved, brs = broad singlet, coupling constant(s) in Hz, integration). ¹³C NMR spectra were recorded on a Bruker AV-400 spectrometer in chloroform-d₃. Chemical shifts are reported in ppm with the internal chloroform signal at 77.0 ppm as a standard. Infrared spectra were recorded on a Nicolet iS 10 spectrometer as thin film and are reported in reciprocal centimeter (cm⁻¹). Mass spectra were recorded with Micromass Q-Exactive Focus mass spectrometer using electron spray ionization. ¹H NMR, and ¹³C NMR are supplied for all compounds: see Supplementary Figs. 1–68. More mechanism studies are supplied: see Supplementary Figs. 69–74. Representative synthetic procedures for the preparation of alkynones are supplied: see Supplementary Fig. 75. General procedure for the synthesis of benzo[6,7]azepino[2,3-b]quinolines 3 is supplied: see Supplementary Fig. 76. General procedure for the synthesis of pyridine-based diones 5 are supplied: see Supplementary Fig. 77. Synthetic applications are supplied: see Supplementary Figs. 78–80. Crystal data are supplied: see Supplementary Tables 1–5. TD-DFT computational data are supplied: see Supplementary Tables 6–15. See Supplementary methods for the characterization data of compounds not listed in this part.