General Procedures

5.2.1. General Procedure A: Manganese(I)-Catalyzed Allylative C−H/C–F Functionalization

A suspension of heteroarene 315 (0.50 mmol, 1.00 equiv), 1H,1H,2H-perfluoroalkene 301 (0.60 mmol, 1.20 equiv), [MnBr(CO)5] (10.3 mg, 7.5 mol %) and K2CO3 (69.1 mg, 0.50 mmol, 1.00 equiv) in 1,4-dioxane (0.50 mL, 1.00 M) was stirred at 80 °C for 20 h. At ambient temperature, the mixture was diluted with EtOAc (3.0 mL) and the solvents were removed in vacuo and the remaining residue was purified by column chromatography on silica gel to afford the desired products 316.

5.2.2. General Procedure B: Manganese(I)-Catalyzed C−H/C–F Functionalization of Heteroarenes with Perfluoroalkenes

A suspension of heteroarene 315/328/332 (0.50 mmol, 1.00 equiv), perfluoroalkene 303 (1.50 mmol, 3.00 equiv), [MnBr(CO)5] (13.7 mg, 10.0 mol %) and K2CO3 (69.0 mg, 0.50 mmol, 1.00 equiv) in 1,4-dioxane (0.50 mL, 1.00 M) was stirred at 100 °C for 20 h. At ambient temperature, the solvent was removed in vacuo and the remaining residue was purified by column chromatography on silica gel to afford the desired products 328/331/333.

5.2.3. General Procedure C: Ruthenium(II)-Catalyzed C–F/C–H Functionalization A suspension of ketimine 340 (0.50 mmol, 1.0 equiv), 1H,1H,2H-perfluoroalkene 301 (1.50 mmol, 3.0 equiv), [RuCl2(p-cymene)]2 (15.3 mg, 5.0 mol %), P(4-C6H4F)3 (31.6 mg, 20 mol %) and K3PO4 (212 mg, 1.0 mmol, 2.0 equiv) in cyclohexane (1.0 mL) was stirred under N2 at 120 °C for 24 h in pressure tube. At ambient temperature, the reaction mixture was diluted with EtOAc (5.0 mL) and HCl (5.0 mL, 1 M) was added. The mixture was stirred for 3 h and extracted with EtOAc (3 x 10.0 mL). After removal of the solvents in vacuo, the remaining residue was purified by column chromatography on silica gel to afford the desired products 307.

5.2.4. General Procedure D: Synthesis of the chiral acid CA5-CA7 and CA10-CA14.

To a solution of (S,S)-diphenylethanediamine (212.3 mg, 1.00 mmol) in CH2Cl2 (4.0 mL) was added an equimolar amount of glyoxylic acid monohydrate (92.1 mg, 1.00 mmol) under vigorous stirring. After 16 h, the solvent was removed to afford (4S,5S)-4,5-diphenylimidazolidine-2- carboxylic acid 408 (265.3 mg, 99% yield) as a yellow solid.

To a solution of 408 in THF/H2O (5 mL, 1:1) at 0 °C, NaHCO3 (252 mg, 3.00 mmol) and acyl chloride (2.10 mmol, 2.1 equiv) were added, and the reaction was allowed to reach ambient temperature. After 16 h, the reaction mixture was diluted with CH2Cl2 (10 mL) and washed with HCl (1 M, 10 mL) solution. The aqueous phase was extracted with CH2Cl2 (3 x 10 mL).

The combined organic phase was washed with brine and dried over Na2SO4 and the solvent was removed under vacuum. The crude mixture was purified via flash chromatography (CH2Cl2

100% to CH2Cl2:CH3OH = 90:10) to afford chiral acids CA5-CA7 and CA10-CA14.

5.2.5. General Procedure E: Cobalt(III)-Catalyzed Asymmetric C−H Alkylation

A suspension of indole 354 (0.50 mmol, 1.00 equiv), alkene 223 (1.50 mmol, 3.00 equiv), [Cp*Co(CO)I2] (23.8 mg, 50.0 µmol, 10.0 mol %), AgSbF6 (34.4 mg, 100 µmol, 20.0 mol %), chiral acid CA5 (48.0 mg, 100 µmol, 20.0 mol %) and Amberlyst 15 (160 mg, 1.50 equiv) in DCE (0.5 mL, 1.0 M) were stirred at 50 °C for 65 h. At ambient temperature, the reaction mixture was diluted with EtOAc (2.0 mL) and Et3N (0.5 mL) was added. The mixture was stirred for 0.5 h and filtered through a short pad of silica and the solvents were removed in vacuo. The crude mixture was purified by flash column chromatography on silica gel to afford the desired product 355.

5.2.6. General Procedure F: Synthesis of Racemic Products for Cobalt(III)-Catalyzed C−H Alkylation

A suspension of indole 354 (0.50 mmol, 1.00 equiv), alkene 223 (1.50 mmol, 3.00 equiv), [Cp*Co(CO)I2] (23.8 mg, 50.0 µmol, 10.0 mol %), AgSbF6 (34.4 mg, 100 µmol, 20.0 mol %), 1-AdCO2H (48.0 mg, 100 µmol, 20.0 mol %) in DCE (0.5 mL, 1.0M) were stirred at 50 °C for

solvents were removed in vacuo. The crude mixture was purified by flash column chromatography on silica gel to afford the racemic product 355.

5.2.7. General Procedure G: Traceless Removable of Directing Group for Cobalt(III)-Catalyzed C−H Alkylated Products

To a solution of 355 (0.2 mmol, 1.00 equiv) in CH2Cl2 (0.5 mL) was added MeOTf (36.1 mg, 1.10 equiv) dropwise at 0 °C. After 30 min, the mixture was allowed to warm up to 25 °C and stirred for 6 h. After removal of the solvent in vacuo, Pd(OH)2/C (7.7 mg, 10 wt.-%) and ammonium formate (126 mg, 2.00 mmol, 10.0 equiv) were added. The mixture was diluted with MeOH (1.0 mL) and stirred at 60 °C for 6 h. After addition of EtOAc (5.0 mL) at ambient temperature, the mixture was filtered through a short pad of celite^® and the solvents were removed in vacuo. The crude mixture was purified by flash column chromatography on silica gel to yield 357.

5.2.8. General Procedure H: Ruthenium(II)-Catalyzed Asymmetric C−H Alkylation for the Synthesis of Tetrahydrocarbazoles

A suspension of indole 362 (0.25 mmol, 1.00 equiv), [RuCl2(p-cymene)]2 (7.7 mg, 5.0 mol %), AgSbF6 (17.2 mg, 20 mol %), chiral acid CA14 (25.2 mg, 20 mol %) in PhMe (0.50 mL) were stirred at 25 °C for 12 h. The reaction mixture was diluted with EtOAc (2.0 mL) and the solvent was removed in vacuo. The crude mixture was purified by column chromatography on silica gel to afford the desired product 363.

5.2.9. General Procedure I: Synthesis of Racemic Products for Ruthenium(II)-Catalyzed C−H Alkylation

A suspension of indole 362 (0.10 mmol, 1.00 equiv), [RuCl2(p-cymene)]2 (3.1 mg, 5.0 mol %), AgSbF6 (6.9 mg, 100 µmol, 20 mol %), 1-AdCO2H (18.0 mg, 1 equiv) in PhMe (0.50 mL) were stirred at 50 °C for 12 h. At ambient temperature, the reaction mixture was diluted with EtOAc (2.0 mL) and the solvents were removed in vacuo. The crude mixture was purified by column chromatography on silica gel to afford the racemic products rac-363.

5.2.10. General Procedure J: Copper-catalyzed Alkyne Annulation by C–H Alkynylation The electrocatalysis was carried out in an undivided cell, with a RVC anode (10 mm × 15 mm

× 6 mm) and a platinum cathode (10 mm × 15 mm × 0.25 mm). Benzamide 229 (0.25 mmol, 1.0 equiv), alkyne 255 (0.50 mmol, 2.0 equiv), NaOPiv (31 mg, 0.25 mmol, 1.0 equiv) and

Cu(OAc)2∙H2O (2.5 mg, 5.0 mol %) were placed in a 10 mL cell and dissolved in DMA (4.0 mL). Electrocatalysis was performed at 100 °C with a constant current of 6.0 mA maintained for 6 h. At ambient temperature, saturated aqueous NaHCO3 (4.0 mL) was added. The RVC anode was washed with EtOAc (3 × 10 mL) in an ultrasonic bath. The washings were added to the reaction mixture and the combined phases were extracted with EtOAc (4 × 10 mL), then dried over Na2SO4. Evaporation of the solvent and subsequent column chromatography on silica gel afforded the corresponding products 256.

5.2.11. General Procedure K: Cobaltaelectro-Catalyzed C–H Allylation

The electrolysis was carried out in an undivided cell with a GF anode (10 mm × 15 mm × 6 mm) and a platinum cathode (10 mm × 15 mm × 0.25 mm). Co(OAc)2∙4H2O (12.7 mg, 0.05 mmol, 10 mol %), NaOPiv (124.0 mg, 1.0 mmol, 2.0 equiv), n-Bu4NPF6 (97.0 mg, 0.25 mmol, 0.50 equiv) and benzamide 229 (0.50 mmol, 1.0 equiv) were dissolved in GVL (4.0 mL) and the alkene 223 (1.5 mmol, 3.0 equiv) was added sequentially. At 100 °C, electrolysis was conducted with a constant current of 4.0 mA for 14 h. The mixture was transferred to a flask and the electrodes were rinsed with acetone (3 × 5.0 mL). Then the combined solvent was removed under reduced pressure, the residue was diluted with EtOAc (10 mL) and stirred with NaOH (aq) (2 M, 20 mL) for 2 h. The mixture was extracted with water (3 × 20 mL) and successively with EtOAc (3 × 20 mL), then the organic layer was dried over Na2SO4. After evaporation of the solvent under vacuo, subsequent column chromatography on silica gel (n-hexane/EtOAc) yielded the desired product 242.

5.2.12. General Procedure L: Atroposelective Palladaelectro-catalyzed C–H Olefination The electrocatalysis was carried out in an undivided cell, with a GF anode (10 mm × 15 mm × 6 mm) and a platinum cathode (10 mm × 15 mm × 0.25 mm). Biaryls 73 or 396 (0.20 mmol, 1.0 equiv), acrylates 38 (0.60 mmol, 3 equiv), Pd(OAc)2 (4.49 mg, 10 mol %), L-tert-leucine (5.24 mg, 20 %) and LiOAc (26.4 mg, 2 equiv) were placed in a 10 mL cell and dissolved in AcOH (4.5 mL). Electrocatalysis was performed at 60 °C with a constant current of 1.0 mA maintained for 20 h. At ambient temperature, the reaction mixture was diluted with EtOAc.

The GF anode was washed with EtOAc (3 × 10 mL) in an ultrasonic bath. The combined washings were added to the reaction mixture and the solvents were removed in vacuo. The crude mixture was purified by column chromatography on silica gel to yield 74 or 397.

5.2.13. General Procedure M: General Procedure for the Synthesis of Racemic Products The racemic compounds were prepared using rac-D/L-valine as the transient directing groups instead of L-tert-leucine, following the general procedure L.

Figure 4. Electrochemical Reaction set up.

5.3. Manganese(I)-Catalyzed Allylative C−H/C–F Functionalization