Supporting Information of the manuscript " Iridium-Catalyzed Tandem Dehydrogenation/Hydroarylation Approach to Synthetically Versatile C2-Alkenyl N–H Indoles"

1. General Procedures S3 2. Optimization and additional control experiments S4 3. Procedures for the synthesis of reaction precursors S8 4. Ir-catalyzed tandem processes S12 - General procedure B: Tandem dehydrogenation/hydroarylation of N-carbamoyl Indolines 1 with alkynes 2 for the synthesis of indoles 3aa-3ga S12 - General procedure C: Tandem dehydrogenation/hydroarylation of N-carbamoyl Indolines 1 with alkenes 5 for the synthesis of indoles 6aa-6af S22 5. Synthetic transformations based on by transition metal catalyzed C-H functionalizations S24 - Initial [4+2] annulation attempts using indole 3aa and several alkynes with palladium catalysis. S24 - Pd-promoted olefin isomerization of (E)-2-(1,2-diphenylvinyl)-1H-indole E-3aa to Z-3aa S25 - General procedure D: Rh-catalyzed [4+2] annulation between C2-alkenylated NH-indoles 3 and alkynes 2, for the synthesis of pyrido[1,2-a]indoles (7ab-7mb, exemplified for 7ab) S25 - General procedure E: Rh-catalyzed [4+1] annulation between C2-alkenylated NH-indoles 3 and CO, for the synthesis of pyrrolo[1,2-a]indole-3-one (8aa-8ai, exemplified for 8aa) S29 - Rh-catalyzed [4+1] annulation between (E)-2-(1,2-diphenylvinyl)-1H-indole 3aa and dimetildiazomalonate 9a, for the synthesis of pyrrolo[1,2-a]indole-3,3-diester 10aa S31 - General procedure F: Ir-catalyzed [4+2] annulation between C2-alkenylated NH-indoles 3 and diazo derivatives 9, for the synthesis of pyridoindoles (11ab-11ib, exemplified for 11ab) S32 - General procedure G: Rh-catalyzed C-H functionalization between C2-alkenylated NH indoles 3 and methyl acrylate, for the synthesis of (E,E)-dienes 12aa-12am (exemplified for 12aa) S35 - General procedure H: Rh-catalyzed annulation between C2-alkenylated NH-indoles 3 and methyl acrylate, for the synthesis of carbazoles 13aa-13ah (exemplified for 13aa) S37 - General procedure I: Ru-catalyzed dehydrogenative ring closure for the synthesis of benzo[c]carbazoles 14aa-ah from C2-alkenylated NH-indoles 3 S40 6. Metal-free synthetic manipulations C2-alkenyl indoles 3 S43 - Desilylation of (Z)-2-(2-phenyl-1-(trimethylsilyl)vinyl)-1H-indole 3ao S43 - Acid-promoted synthesis of carbazole 15 S43 - Acid-promoted synthesis of carbazole 16 S44 - Synthesis of γ-carboline 17 S44 7. Tandem protocol for the synthesis of Sorazolon E S45 8. NMR spectra S47 9. References S121