A General Copper Catalyst for Photoredox Transformations of Organic Halides

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1 Supporting Information A General Copper Catalyst for Photoredox Transformations of Organic Halides Bastien Michelet, a Christopher Deldaele, a Sofia Kajouj, b Cécile Moucheron b and Gwilherm Evano a, * a Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université libre de Bruxelles (ULB), Avenue F. D. Roosevelt 50, CP160/06, 1050 Brussels, Belgium. b Laboratoire de Chimie Organique et Photochimie, Service de Chimie et PhysicoChimie Organiques, Université libre de Bruxelles (ULB), Avenue F. D. Roosevelt 50, CP160/08, 1050 Brussels, Belgium. General Information.... S2 Experimental Procedures and Characterization Data: Synthesis and Characterization of [(DPEphos)(bcp)Cu]PF6... S4 Experimental Procedures and Characterization Data: Unreported Starting Materials... S12 Experimental Procedures and Characterization Data: Copper-Catalyzed Photoredox Reduction of Aryl Halides... S24 Experimental Procedures and Characterization Data: Copper-Catalyzed Photoredox Cyclization of Aryl Iodides... S25 Experimental Procedures and Characterization Data: Copper-Catalyzed Photoredox Transformations of Alkyl Halides... S32 Experimental Procedures and Characterization Data: Copper-Catalyzed Photoredox Direct Arylation of (Hetero)arenes with Aryl Halides... S34 1 H and 13 C NMR Spectra... S42 References... S98 S1

2 General Information All reactions were carried out in oven-dried glassware under an argon atmosphere employing standard techniques in handling air-sensitive materials. All solvents were reagent grade. Acetonitrile was freshly distilled from calcium hydride under argon and degassed by using the freeze-pump-thaw method. N,N -diisopropylethylamine (ipr2net) was distilled from KOH under argon and stored away from light. Tetrakisacetonitrile copper(i) hexafluorophosphate was purchased from Aldrich and used as supplied. Bathocuproine (bcp) and bis[(2-diphenylphosphino)phenyl] ether (DPEphos) were purchased from Acros and used as supplied. All other reagents were used as supplied. Reactions were magnetically stirred and monitored by thin layer chromatography using Merck- Kiesegel 60F254 plates. Flash chromatography was performed with silica gel 60 (particle size µm) supplied by Merck. Yields refer to chromatographically and spectroscopically pure compounds unless otherwise stated. Photoinduced copper-catalyzed reactions were performed in a Luzchem CCP-4V photoreactor using 420 nm light tubes supplied by Luzchem or using commercially available blue LEDs strips as the source of light. Proton NMR spectra were recorded using an internal deuterium lock at ambient temperature on Bruker 300 MHz or Varian 400 MHz spectrometers. Internal reference of H 7.26 was used for CDCl3. Data are presented as follows: chemical shift (in ppm on the scale relative to TMS = 0), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, quint. = quintuplet, m = multiplet, br. = broad, app. = apparent), coupling constant (J/Hz) and integration. Resonances that are either partially or fully obscured are denoted obscured (obs.). Carbon-13 NMR spectra were recorded at 75 MHz using CDCl3 ( C 77.16) as internal reference. Fluorine-19 NMR spectra were recorded at 377 MHz. Melting points were recorded on a Stuart Scientific Analogue SMP11. Infrared spectra were recorded on a Bruker Alpha (ATR). High-resolution mass-spectra were obtained on an Agilent Technologies QTOF 6520 spectrometer. Absorption spectra were recorded on UV-Visible Perkin Elmer Lambda 40 spectrophotometer. Emission spectra were recorded with a Shimadzu RF-5301PC spectrofluorimeter equipped with a 150 W Xenon lamp as excitation source and a Hamamatsu R928 phototube as a detector. Corrections of the emission spectra were achieved by measuring the spectrum of a calibrated tungsten-halogen Edinburgh Analytical Instrument lamp of 10 Watts (200 to 2600 nm). The luminescence lifetimes were measured by time-correlated single-photon-counting (TC-SPC) with a LifeSpec-II Edinburgh Instruments equipped Peltier-cooled photomultiplier (R3809U-50, Hamamatsu). The sample was excited via a laser diode (PDL445, <100ps) and the emission was measured at the maximum of emission of the complex. The data were collected by a multichannel analyser with a number of counts in the first channel (t = 0) minimum equal to The resulting decays were analyzed with the Edinburgh Instruments with F900 CDT software. They were deconvoluted for the instrumental response and fitted to exponential functions based on non-linear least squares regressions using a modified Marquardt S2

3 algorithm thanks to Wavemetrics Igor Pro version 6.37 software. The reduced χ2, weighted residuals and autocorrelation function were employed for judging the quality of the fits. Cyclic voltammetry was carried out on a carbon disk working electrode (approximate area = 3 mm 2 ), in dry and degassed acetonitrile with tetrabutylammonium hexafluorophosphate (0.1 M) as supporting electrolyte. The potential of the working electrode was controlled by an Autolab PGSTAT 100 (Eco Chemie B. V., Utrecht, The Netherlands) potentiostat through a PC interface with a scan rate of 10 mv.s -1 between -2 and +2 V vs SCE. The counter electrode was a platinum wire (spiral diameter: 15 mm, spiral height: 70 mm), and the reference electrode a Saturated Calomel Electrode (SCE). All measurements were performed in a single compartment cell. Copper complexes [(phen)2cu]cl, S1 [(dmp)2cu]cl, S2 [(dap)2cu]cl, S3 [(DPEphos)2Cu]PF6, S4 [(bcp)2cu]pf6, S5 [(binc)(dmp)cu]pf6, S6 [(binc)(dap)cu]pf6, S6 [(Xantphos)(dmp)Cu]PF6, S7 [(Xantphos)(bcp)Cu]PF6, S8 [(DPEphos)(dap)Cu]PF6, S6 [(DPEphos)(dmp)Cu]PF6, S8 have been prepared according to reported procedures. Compounds 3a, S9 3b, S10 3c, S11 3i, S12 5, S13 7, S14 9 S15 and 11 S16 have been prepared according to reported procedures. Dicyclohexylisobutylamine (Cy2NiBu) have been prepared following a reported procedure. S17 S3

4 Experimental Procedure and Characterization Data: Synthesis and Characterization of [(DPEphos)(bcp)Cu]PF6 [(DPEphos)(bcp)Cu]PF 6. A mixture of tetrakisacetonitrile copper(i) hexafluorophosphate (373 mg, 1.00 mmol) and bis[(2-diphenylphosphino)phenyl] ether (DPEphos, 539 mg, 1.00 mmol) in dry DCM (80 ml) was stirred for two hours at room temperature under argon. A solution of bathocuproine (bcp, 360 mg, 1.00 mmol) in DCM (20 ml) was then added and the mixture was stirred for an additional hour. The mixture was then filtered through a pad of Celite and concentrated to ca ml under reduced pressure. The concentrate was then added dropwise to 100 ml of Et2O with vigorous stirring. The precipitate was collected by filtration and dried under vacuum to afford [(DPEphos)(bcp)Cu]PF6 (1.1 g, 0.99 mmol, 99%) as a bright yellow solid. The spectroscopic data correspond to those previously described in the litterature. S8 S4

5 Absorbance (arb. unit) Absorbance (arb. unit) Absorption and Emission Spectra 1,8 1,6 1,4 1,2 1 0,8 0,6 0,4 0, Wavelength (nm) Figure S1: UV-visible absorption spectrum of [(DPEPhos)(bcp)Cu]PF6 recorded at ambient temperature under argon in MeCN (10-4 M). 1,8 1,6 1,4 1,2 1 0,8 0,6 0,4 0, Wavelength (nm) Figure S2: UV-visible absorption spectrum of [(bcp)2cu]pf6 recorded at ambient temperature under argon in MeCN (10-4 M). S5

6 Signal intensity Emission intensity (arb. unit) Wavelength (nm) Figure S3: Visible emission spectrum of [(DPEPhos)(bcp)Cu]PF6 obtained by excitation at 445 nm and recorded at ambient temperature under argon in MeCN (10-4 M). Luminescent Decay Profile 0 = 819 ns. Time (ns) Figure S4: Luminescent decay of [(DPEPhos)(bcp)Cu]PF6 measured at ambient temperature under argon in MeCN (10-4 M) and recorded at 545 nm (λ exc = 445nm). S6

7 Photostability studies t = 0 h t = 8 h t = 24 h Figure S5: 1 H NMR monitoring of the stability of [(DPEPhos)(bcp)Cu]PF6 in MeCN-d 3 at ambient temperature in the dark. S7

8 t = 0 h t = 8 h t = 24 h [(bcp)2cu]pf6 Figure S6: 1 H NMR monitoring of the stability of [(DPEPhos)(bcp)Cu]PF6 in MeCN-d 3 at ambient temperature under 420 nm irradiation. S8

9 Absorbance (arb. unit) 0,7 0,6 0,5 t = 0h t = 2h t = 4h t = 6h t = 8h t = 1h t = 3h t = 5h t = 7h t = 22h 0,4 0,3 0,2 0, Wavelength (nm) Figure S7: UV-visible absorption monitoring of the stability of [(DPEPhos)(bcp)Cu]PF6 under blue LEDs irradiation. Spectra recorded at ambient temperature under argon in MeCN (10-4 M). S9

10 Cyclic voltammetry and determination of the redox potentials of [(DPEPhos)(bcp)Cu)]PF x x x 10-5 Current [A] -2-1,5-1 -0,5 0 0,5 1 1, x x x 10-5 Potential [V vs SCE] Figure S8: Cyclic voltammogram of [(DPEPhos)(bcp)Cu]PF6 in extra dry MeCN (10-3 M) using tetrabutylammonium hexafluorophosphate (0.1M) as supporting electrolyte at scan rate of 10 mv.s -1. E½ (Cu II /Cu I ) E½ (Cu I /Cu 0 ) [a] E0-0 E½ (Cu II /Cu I *) [b] E½ (Cu I */Cu 0 ) [c] [V vs SCE] [V vs SCE] [V] [V vs SCE] [V vs SCE] [a] Estimated from the onset of the emission band. [b] E ½ (Cu II /Cu I *) = E ½ (Cu II /Cu I ) - E 0-0. [c] E ½ (Cu I */Cu 0 ) = E ½ (Cu I /Cu 0 ) + E 0-0. S10

11 Quenching experiment with ipr 2NEt as quencher. Figure S9: Quenching of [(DPEphos)(bcp)Cu]PF6* by ipr2net. Inset represents the Stern-Volmer plot for the quenching of [(DPEphos)(bcp)Cu]PF6* by ipr2net. Quenching experiment with iodobenzene as quencher. Figure S10: Quenching of [(DPEphos)(bcp)Cu]PF6* by iodobenzene. Inset represents the Stern-Volmer plot for the quenching of [(DPEphos)(bcp)Cu]PF6* by iodobenzene. S11

12 Experimental Procedures and Characterization Data: Unreported Starting Materials Methyl 4-(N-allylacetamido)-3-iodobenzoate 3d. To a solution of methyl 4-amino-3-iodobenzoate (1.0 g, 3.61 mmol) in acetic anhydride (8 ml) were added few drops of concentrated sulfuric acid. The mixture was stirred at room temperature for 15 min and was then diluted with ethyl acetate (20 ml). The organic phase was washed with water, aq. satd NaHCO3 solution, brine and dried over MgSO4. After evaporation of the volatiles, the residue was recrystallized from ethanol to afford methyl 4-acetamido-3-iodobenzoate (825 mg, 2.59 mmol, 72%) as a white solid. This compound has been previously reported. S18 To a solution of methyl 4-acetamido-3-iodobenzoate (680 mg, 2.13 mmol) in dry THF (10 ml) was added NaH (60% in mineral oil, 94 mg, 2.34 mmol) at 0 C under argon. The mixture was stirred until the evolution of gas subsided and allyl bromide (220 µl, 2.56 mmol) was added dropwise. The mixture was stirred overnight at room temperature and then quenched with water. The layers were separated and the aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 75/25) to afford methyl 4-(N-allylacetamido)-3-iodobenzoate 3d (410 mg, 1.14 mmol, 54%) as a pale yellow solid. Mp: 71 C; 1 H NMR (300 MHz, CDCl3): 8.58 (d, J = 1.8 Hz, 1H), 8.03 (dd, J = 8.1 and 1.8 Hz, 1H), 7.22 (d, J = 8.1 Hz, 1H), 5.86 (dddd, J = 17.0, 10.1, 7.8 and 5.5 Hz, 1H), 5.09 (d, J = 10.1 Hz, 1H), 5.01 (ddt, J = 17.0, 1.2 and 1.2 Hz, 1H), 4.82 (app. ddt, J = 14.7, 5.5 and 1.2 Hz, 1H), 3.92 (s, 3H), 3.59 (dd, J = 14.7 and 7.8 Hz, 1H), 1.78 (s, 3H); 13 C NMR (75 MHz, CDCl3): 169.3, 164.8, 148.7, 141.4, 132.4, 131.5, 130.7, 130.5, 119.2, 100.5, 52.7, 51.0, 23.0; IR (ATR): νmax 1714, 1657, 1383, 1282, 1247, 1118 cm -1 ; ESIHRMS m/z calcd for C13H15INO3 [M+H] , found S12

13 N-Allyl-4-cyano-2-iodoacetanilide 3e. To a solution of 4-cyano-2-iodoaniline (1.0 g, 4.10 mmol) in acetic anhydride (8 ml) were added few drops of concentrated sulfuric acid. The mixture was stirred at room temperature for 15 min and water was added (10 ml). The white precipitate was filtered and rinsed with small portions of ethanol to afford 4-cyano-2-iodoacetanilide (800 mg, 2.80 mmol, 68%) as a white solid. This compound has been previously reported. S19 To a solution of 4-cyano-2-iodoacetanilide (400 mg, 1.40 mmol) in dry THF (15 ml) was added NaH (60% in mineral oil, 62 mg, 1.54 mmol) at 0 C under argon. The mixture was stirred until the evolution of gas subsided and allyl bromide (145 µl, 1.68 mmol) was added dropwise. The mixture was stirred overnight at room temperature and then quenched with water. The layers were separated and the aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 75/25) to afford N-allyl-4-cyano-2-iodoacetanilide 3e (240 mg, 0.74 mmol, 53%) as a white solid. Mp: 146 C; 1 H NMR (300 MHz, CDCl3): 8.21 (d, J = 1.8 Hz, 1H), 7.67 (dd, J = 8.1 and 1.8 Hz, 1H), 7.23 (s, 1H), 5.84 (dddd, J = 17.1, 10.1, 8.0 and 5.4 Hz, 1H), 5.10 (d, J = 10.1 Hz, 1H), 5.01 (ddt, J = 17.1, 1.2 and 1.2 Hz, 1H), 4.81 (app. ddt, J = 14.7, 5.4 and 1.2 Hz, 1H), 3.56 (dd, J = 14.7 and 8.0 Hz, 1H), 1.77 (s, 3H); 13 C NMR (75 MHz, CDCl3): 169.0, 149.0, 143.6, 133.2, 132.2, 131.2, 119.6, 116.3, 114.1, 101.3, 51.1, 23.1; IR (ATR): νmax 3051, 2232, 1645, 1478, 1397, 1298, 1287, 935 cm -1 ; ESIHRMS m/z calcd for C12H12IN2O [M+H] , found S13

14 N-Allyl-5-fluoro-2-iodoacetanilide 3f. To a solution of 5-fluoro-2-iodoaniline (500 mg, 1.57 mmol) in DCM (10 ml) were added acetic anhydride (241 µl, 2.50 mmol) and Et3N (732 µl, 5.25 mmol). The mixture was stirred for three days at room temperature and then concentrated under reduced pressure. The residue was purified by chromatography over silica gel (petroleum ether/etoac: 90/10) to afford 5-fluoro-2-iodoacetanilide (376mg, 1.18 mmol, 75%). This compound has been previously reported. S20 To a solution of 5-fluoro-2-iodoacetanilide (376 mg, 1.18 mmol) in dry THF (15 ml) was added NaH (60% in mineral oil, 65 mg, 1.62 mmol) at 0 C under argon. The mixture was stirred until the evolution of gas subsided and allyl bromide (140 µl, 1.62 mmol) was added dropwise. The mixture was stirred overnight at room temperature and then quenched with water. The layers were separated and the aqueous phase was extracted three times with Et2O. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 80/20) to afford N-allyl-5-fluoro-2-iodoacetanilide 3f (270 mg, 0.85 mmol, 72%) as a pale yellow solid. Mp: 33 C; 1 H NMR (300 MHz, CDCl3): 7.87 (dd, J = 8.8 and 6.0 Hz, 1H), (m, 2H), 5.86 (dddd, J = 17.1, 10.1, 7.8 and 5.5 Hz, 1H), 5.11 (d, J = 10.1 Hz, 1H), 5.04 (ddt, J = 17.0, 1.3 and 1.3 Hz, 1H), 4.80 (app. ddt, J = 14.7, 5.5 and 1.3 Hz, 1H), 3.56 (dd, J = 14.7 and 7.8 Hz, 1H), 1.79 (s, 3H); 13 C NMR (75 MHz, CDCl3): 169.5, (d, J = Hz), (d, J = 9.2 Hz), (d, J = 8.6 Hz), 132.4, 119.1,118.2 (d, J = 22.0 Hz), (d, J = 21.3 Hz), 93.9 (d, J = 3.4 Hz), 51.0, 22.9 ; 19 F NMR (377 MHz, CDCl3): (app. td, J = 8.2 and 6.4 Hz); IR (ATR): νmax 2927, 1667, 1465, 1380, 1182, 928, 814 cm -1 ; ESIHRMS m/z calcd for C11H12FINO [M+H] , found S14

15 N-Allyl-2-iodo-5-methoxyacetanilide 3g. Following a reported procedure, S21 1-iodo-4-methoxy-2- nitrobenzene (1.0 g, 3.6 mmol) and activated charcoal (9 mg, 720 µmol) were added to a solution of FeCl3. 6H2O (15 mg, 54 µmol) in MeOH. The mixture was heated to reflux and hydrazine monohydrate (475 µl, 10.8 mmol) was added dropwise. The mixture was stirred under reflux overnight and then filtered through a pad of Celite which was rinsed with DCM. After concentration under reduced pressure, the residue was purified by chromatography over silica gel (petroleum ether/etoac: 95/5 to 90/10) to afford 2-iodo-5- methoxyaniline as a pale yellow oil (464 mg, 1.86 mmol, 52%). To a solution of 2-iodo-5-methoxyaniline (464 mg, 1.86 mmol) in acetic anhydride (4 ml) were added few drops of concentrated sulfuric acid. The mixture was stirred at room temperature for 1 h and was then diluted with ethyl acetate (20 ml). The organic phase was washed with water, aq. satd NaHCO3 solution, brine and dried over MgSO4. After evaporation of the volatiles, the residue was recrystallized from ethanol to afford 2- iodo-5-methoxacetanilide (345 mg, 1.19 mmol, 64%) as a white solid. This compound has been previously reported. S20 To a solution of 2-iodo-5-methoxacetanilide (345 mg, 1.19 mmol) in dry THF (10 ml) was added NaH (60% in mineral oil, 57 mg, 1.43 mmol) at 0 C under argon. The mixture was stirred until the evolution of gas subsided and allyl bromide (155 µl, 1.79 mmol) was added dropwise. The mixture was stirred overnight at room temperature and then quenched with water. The layers were separated and the aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 90/10 to 80/20) to afford N-allyl-2-iodo-5-methoxyacetanilide 3g (360 mg, 1.09 mmol, 91%) as a pale yellow solid. Mp: 47 C; 1 H NMR (300 MHz, CDCl3): 7.75 (d, J = 8.7 Hz, 1H), 6.72 (d, J = 2.9 Hz, 1H), 6.66 (dd, J = 8.7 and 2.9 Hz, 1H), 5.88 (dddd, J = 17.1, 10.2, 7.7 and 5.5 Hz, 1H), 5.09 (obs. d, J = 10.2 Hz, 1H), 5.04 (obs. d, J = 17.1 Hz, 1H), 4.78 (dd, J = 14.7, 5.5 Hz, 1H), 3.77 (s, 3H), 3.56 (dd, J = 14.7 and 7.7 Hz, 1H), 1.79 (s, 3H); 13 C NMR (75 MHz, CDCl3): 169.9, 160.7, 145.5, 140.2, 132.8, 118.7, 116.7, 115.8, 88.6, 55.7, 51.1, 22.8; IR (ATR): νmax 2933, 1644, 1468, 1299, 1207, 817 cm -1 ; ESIHRMS m/z calcd for C12H15INO2 [M+H] , found S15

16 Methyl (E)-4-[N-(2-iodophenyl)acetamido]but-2-enoate 3h. To a solution of 2-iodoacetanilide (280 mg, 1.07 mmol) in THF (10 ml) was added NaH (60% in mineral oil, 64 mg, 1.60 mmol) at room temperature. Methyl (E)-4-bromobut-2-enoate (320 µl, 2.40 mmol) was then added and the mixture was stirred under reflux overnight. Water (10 ml) was added and the aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 90/10 to 70/30) to afford methyl (E)-4-(N-(2-iodophenyl)acetamido)but-2-enoate 3h (273 mg, 0.76 mmol, 71%) as a colorless oil. 1 H NMR (300 MHz, CDCl3): 7.94 (d, J = 8.0 and 1.4 Hz, 1H), 7.40 (td, J = 7.6 and 1.4 Hz, 1H), 7.19 (dd, J = 7.9 and 1.6 Hz, 1H), 7.08 (dt, J = 7.6 and 1.6 Hz, 1H), 6.95 (ddd, J = 15.7, 7.3 and 5.5 Hz, 1H), 5.85 (dt, J = 15.7 and 1.5 Hz, 1H), 4.95 (ddd, J = 15.7, 5.5 and 1.8 Hz, 1H), (obs. m, 1H), 3.71 (s, 3H), 1.80 (s, 3H); 13 C NMR (75 MHz, CDCl3): 170.2, 166.4, 144.7, 142.4, 140.5, (2C), 129.9, 123.6, 100.3, 51.7, 49.4, 22.7; IR (ATR): νmax 2950, 1722, 1666, 1278, 1173, 1019, 976, 750 cm -1 ; ESIHRMS m/z calcd for C13H15INO3 [M+H] , found Acetyl-O-allyl-2-iodophenol 3j. To a solution of 4-acetyl-2-iodophenol (548 mg, 2.09 mmol) in acetone (10 ml) were successively added K2CO3 (580 mg, 4.20 mmol) and allyl bromide (270 µl, 3.15 mmol). The mixture was stirred under reflux overnight. The mixture was allowed to cool to room temperature, filtered through Celite (rinsed with Et2O) and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 90/10 to 80/20) to afford 4-acetyl-O-allyl-2-iodophenol 3j (500 mg, 1.66 mmol, 79%) as a pale yellow solid. Mp: 60 C; 1 H NMR (300 MHz, CDCl3): 8.38 (d, J = 2.3 Hz, 1H), 7.91 (dd, J = 8.6 and 2.3 Hz, 1H), 6.81 (d, J = 8.6 Hz, 1H), 6.05 (ddt, J = 17.3, 10.6 and 4.8 Hz, 1H), 5.52 (ddt, J = 17.3, 1.5 and 1.5 Hz, 1H), 5.34 (ddt, J = 10.6, 1.5 and 1.5 Hz, 1H), 4.66 (app. dt, J = 4.8 and 1.6 Hz, 2H), 2.54 (s, 3H); 13 C NMR (75 MHz, CDCl3): 195.6, 160.8, 140.3, 132.0, 131.8, 130.5, 118.3, 111.4, 86.5, 69.9, 26.4; S16

17 IR (ATR): νmax 1664, 1588, 1258, 993, 800 cm -1 ; ESIHRMS m/z calcd for C11H12IO2 [M+H] , found Methyl 4-(allyloxy)-3-iodobenzoate 3k. To a solution of methyl 4-hydroxy-3-iodobenzoate (901 mg, 3.24 mmol) in DMF (10 ml) was added NaH (60% in mineral oil, 156 mg, 3.89 mmol) at room temperature. The mixture was stirred for one hour and allyl bromide (337 µl, 3.89 mmol) was added. The mixture was stirred overnight at room temperature. The reaction was quenched with water and EtOAc was added. The layers were separated and the aqueous phase was extracted three times with EtOAc. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 90/10) to afford methyl 4-(allyloxy)- 3-iodobenzoate 3k (765 mg, 2.40 mmol, 74%) as a white solid. Mp: C; 1 H NMR (300 MHz, CDCl3): 8.45 (d, J = 2.1 Hz, 1H), 7.97 (dd, J = 8.6 and 2.1 Hz, 1H), 6.79 (d, J = 8.6 Hz, 1H), 6.05 (ddt, J = 17.3, 10.6 and 4.8 Hz, 1H), 5.52 (ddt, J = 17.3, 1.5 and 1.5 Hz, 1H), 5.34 (ddt, J = 10.6, 1.5 and 1.5 Hz, 1H), 4.65 (app. dt, J = 4.8 and 1.5 Hz, 2H), 3.88 (s, 3H); 13 C NMR (75 MHz, CDCl3): 165.6, 160.8, 141.2, 131.9, 131.6, 124.5, 118.3, 111.3, 86.0, 69.9, 52.3; IR (ATR): νmax 2943, 1715, 1698, 1592, 1434, 1266, 1122, 995, 763 cm -1 ; ESIHRMS m/z calcd for C11H12IO3 [M+H] , found S17

18 O-Allyl-4-cyano-2-iodophenol 3l. To a solution of 4-cyanophenol (2.4 g, 20 mmol) in NH4OH (25% aq. solution, 200 ml) were quickly added a solution of KI (1.7 g, 10 mmol) and I2 (5.0 g, 20 mmol) in water (200 ml). The mixture was stirred at room temperature overnight and concentrated aq. solution of HCl (350 ml) was added to acidify the solution to ph = 1. The precipitate was collected by filtration and dissolved in ethyl acetate (100 ml). The organic phase was washed with a satd aq. solution of Na2S2O3 (50 ml), water, brine and dried over MgSO4. The solution was dried under vacuum to afford 4-cyano-2-iodophenol (3.3 g, 13.3 mmol, 67%) as a colorless solid. This compound has been previously reported. S22 To a solution of 4-cyano-2-iodophenol (980 mg, 4.00 mmol) in acetone (12 ml) were successively added K2CO3 (1.1 g, 8.0 mmol) and allyl bromide (520 µl, 6.0 mmol). The mixture was stirred under reflux overnight. The mixture was allowed to cool to room temperature, filtered through Celite (rinsed with ethyl acetate) and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 95/5 to 90/10) to afford O-allyl-4-cyano-2-iodophenol 3l (1.1 g, 3.8 mmol, 94%) as white crystals. Mp: 99 C; 1 H NMR (300 MHz, CDCl3): 8.05 (d, J = 2.0 Hz, 1H), 7.60 (dd, J = 8.6 and 2.0 Hz, 1H), 6.82 (d, J = 8.6 Hz, 1H), 6.04 (ddt, J = 17.3, 10.6 and 4.8 Hz, 1H), 5.52 (ddt, J = 17.3, 1.5 and 1.5 Hz, 1H), 5.36 (ddt, J = 10.6, 1.5 and 1.5 Hz, 1H), 4.67 (app. dt, J = 4.8 and 1.6 Hz, 2H); 13 C NMR (75 MHz, CDCl3): 160.7, 143.0, 134.0, 131.5, 118.7, 117.7, 112.0, 106.1, 86.6, 70.1; IR (ATR): νmax 2226, 1588, 1481, 1254, 995, 810 cm -1 ; ESIHRMS m/z calcd for C10H9INO [M+H] , found S18

19 Dimethyl 2-allyl-2-(2-iodophenyl)malonate 3m. To a solution of dimethyl 2-(2-iodophenyl)malonate S23 (1.0 g, 3.0 mmol) in THF (20 ml) was added NaH (60% in mineral oil, 144 mg, 3.60 mmol) at room temperature. The mixture was stirred until the evolution of gas subsided and allyl bromide (390 µl, 4.50 mmol) was added. A tip of spatula of NaI was added and the mixture was stirred for three days at room temperature. Water (20 ml) was added and the aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 98/2 to 92/8) to afford dimethyl 2-allyl-2-(2-iodophenyl)malonate 3m (750 mg, 2.00 mmol, 67%) as a white solid. Mp: 46 C; 1 H NMR (300 MHz, CDCl3): 7.93 (dd, J = 7.8 and 1.4 Hz, 1H), 7.32 (td, J = 7.7 and 1.4 Hz, 1H), 7.09 (dd, J = 8.0 and 1.6 Hz, 1H), 6.95 (td, J = 7.6 and 1.6 Hz, 1H), 5.76 (ddt, J = 17.1, 10.2 and 7.0 Hz, 1H), 5.05 (ddt, J = 17.3, 1.5 and 1.5 Hz, 1H), 4.93 (ddt, J = 10.1, 2.1 and 1.1 Hz, 1H), 3.79 (s, 6H), 3.27 (app. dt, J = 7.2 and 1.1 Hz, 2H); 13 C NMR (75 MHz, CDCl3): (2C), 142.3, 139.9, 133.6, 130.1, 129.1, 128.1, 118.4, 98.3, 66.7, 53.2 (2C), 39.1; IR (ATR): νmax 2948, 1740, 1722, 1640, 1431, 1260, 1249, 1211, 752 cm -1 ; ESIHRMS m/z calcd for C14H15INaO4 [M+Na] , found S19

20 5-Allyl-5-(2-iodophenyl)-2,2-dimethyl-1,3-dioxane 3n. Following a modified procedure previously reported, S23 diisobutylaluminium hydride (1.2M solution in toluene, 13.3 ml, 16.0 mmol) was added dropwise to a solution of dimethyl 2-allyl-2-(2-iodophenyl)malonate 3m (750 mg, 2.09 mmol) in toluene (2 ml) under argon at -50 C. The reaction was stirred at this temperature overnight and then quenched with a satd aq. solution of NH4Cl. The aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 90/10) to afford 2-allyl-2-(2-iodophenyl)propane-1,3-diol (188 mg, 0.59 mmol, 28%) as a white solid. To a solution of 2-allyl-2-(2-iodophenyl)propane-1,3-diol (188 mg, 0.59 mmol) and 2,2-dimethoxypropane (160 µl, 1.30 mmol) in THF (3 ml) was added p-tsoh. H2O (57 mg, 0.30 mmol) and the mixture was stirred overnight at room temperature. Water (5 ml) was added and the aqueous phase was extracted three times with Et2O. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 90/10) to afford 5-allyl-5-(2-iodophenyl)-2,2-dimethyl-1,3-dioxane 3n (204 mg, 0.57 mmol, 97%) as a colorless oil. 1 H NMR (300 MHz, CDCl3): 7.99 (dd, J = 7.8 and 1.4 Hz, 1H), 7.32 (td, J = 7.6 and 1.4 Hz, 1H), 7.23 (dd, J = 8.0 and 1.6 Hz, 1H), 6.89 (td, J = 7.4 and 1.8 Hz, 1H), 5.32 (ddt, J = 17.1, 10.0 and 7.3 Hz, 1H), 5.06 (ddt, J = 17.1, 2.2 and 1.1 Hz, 1H), 4.93 (ddt, J = 9.9, 2.2 and 1.1 Hz, 1H), 4.33 (A of AB syst., J = 11.7 Hz, 2H), 4.24 (B of AB syst., J = 11.7 Hz, 2H), 3.00 (d, J = 7.3 Hz, 2H), 1.48 (s, 3H), 1.34 (s, 3H); 13 C NMR (75 MHz, CDCl3): 143.8, 142.6, 133.5, 130.4, 128.5, 128.0, 117.9, 98.4, 94.5, 66.5 (2C), 42.0, 35.9, 24.3, 23.6; IR (ATR): νmax 2989, 1638, 1463, 1371, 1201, 1093, 916, 736 cm -1 ; APCIHRMS m/z calcd for C15H20IO2 [M+H] , found S20

21 Methyl 2-(2-iodophenyl)pent-4-enoate 3o. To a solution of dimethyl 2-allyl-2-(2-iodophenyl)malonate 3m (650 mg, 1.74 mmol) in DMSO (2 ml) were added water (67 µl) and NaCl (112 mg, 1.91 mmol). The mixture was heated at 150 C overnight. The solution was allowed to cool to room temperature and was extracted three times with Et2O. The combined organic layers were washed with water, brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 90/10) to afford methyl 2-(2-iodophenyl)pent-4-enoate 3o (346 mg, 1.09 mmol, 63%) as a pale yellow oil. 1 H NMR (300 MHz, CDCl3): 7.86 (d, J = 8.0 Hz, 1H), (m, 2H), 6.95 (ddd, J = 8.0, 6.0 and 3.0 Hz, 1H), 5.77 (ddt, J = 17.1, 10.2 and 6.8 Hz, 1H), 5.09 (ddt, J = 17.1, 1.5 and 1.5 Hz, 1H), 5.02 (d, J = 10.2 Hz, 1H), 4.15 (dd, J = 8.4 and 6.6 Hz, 1H), 3.68 (s, 3H), 2.75 (app. dddt, J = 14.2, 8.4, 7.1 and 1.5 Hz, 1H), 2.75 (app. dddt, J = 14.2, 6.6, 6.6 and 1.1 Hz, 1H); 13 C NMR (75 MHz, CDCl3): 173.5, 141.6, 140.0, 134.9, 129.1, 128.8, 128.1, 117.5, 101.7, 54.8, 52.3, 37.6; IR (ATR): νmax 2950, 1736, 1640, 1466, 1434, 1198, 1168, 1010, 919, 745 cm -1 ; ESIHRMS m/z calcd for C12H14IO2 [M+H] , found (2-Iodophenyl)pent-4-en-1-ol. To a solution of methyl 2-(2-iodophenyl)pent-4-enoate 3o (216 mg, 0.68 mmol) in toluene (0.7 ml) under argon at -50 C was added dropwise diisobutylaluminium hydride (1.2M solution in toluene, 2.3 ml, 2.73 mmol). The reaction was stirred at this temperature for three hours and then quenched with a satd aq. solution of NH4Cl. The aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The residue was then purified by chromatography over silica gel (petroleum ether/etoac: 90/10 to 85/15) to afford 2-(2-iodophenyl)pent-4-en-1-ol (180 mg, 0.62 mmol, 92%) as a colorless oil. 1 H NMR (300 MHz, CDCl3): 7.87 (dd, J = 7.9 and 1.3 Hz, 1H), 7.33 (td, J = 7.6 and 1.3 Hz, 1H), 7.21 (dd, J = 7.9 and 1.8 Hz, 1H), 6.93 (td, J = 7.6 and 1.8 Hz, 1H), 5.76 (ddt, J = 17.1, 10.2 and 6.9 Hz, 1H), (m, 2H), 3.80 (d, J = 6.1 Hz, 2H), 3.37 (app. quint., J = 6.7 Hz, 1H), (m, 2H), 1.40 (br. s, 1H); 13 C NMR (75 MHz, CDCl3): 144.1, 140.1, 136.0, (2C), 127.7, 117.0, 103.1, 65.9, 50.9, 36.4; IR S21

22 (ATR): νmax 3076, 2923, 2175, 1683, 1640, 1465, 1435, 1008, 915, 752 cm -1 ; ESIHRMS m/z calcd for C11H14IO [M+H] , found Iodo-2-(1-trimethylsilyloxy-pent-4-en-2-yl)benzene 3p. To a solution of 2-(2-iodophenyl)pent-4-en-1-ol (165 mg, 0.57 mmol) in THF (1 ml) were added Et3N (160 µl, 1.15 mmol) and TMS-Cl (146 µl,1.15 mmol). The mixture was stirred at room temperature for 3 h. The solution was concentrated under reduced pressure and diluted with Et2O. The organic phase was filtered through a pad of Celite, washed with water, brine, dried over MgSO4 and concentrated under vacuum to afford 1-iodo-2-(1-trimethylsilyloxy-pent-4-en-2-yl)benzene 3p (181 mg, 0.50 mmol, 88%) as a colorless oil. 1 H NMR (300 MHz, CDCl3): 7.84 (dd, J = 7.9 and 1.2 Hz, 1H), 7.29 (obs. td, J = 7.6 and 1.2 Hz, 1H), 7.17 (dd, J = 7.9 and 1.7 Hz, 1H), 6.89 (td, J = 7.6 and 1.7 Hz, 1H), 5.71 (ddt, J = 17.1, 10.1 and 6.9 Hz, 1H), (m, 2H), 3.72 (A of ABX syst., J = 10.2 and 5.3 Hz, 1H), 3.61 (B of ABX syst., J = 10.2 and 6.7 Hz, 1H), 3.30 (m, 1H), 2.63 (A of ABXYZ2 syst., J = 14.4, 6.8, 6.1 and 1.4 Hz, 1H), 2.38 (B of ABXYZ2 syst., J = 14.4, 8.6, 7.0 and 1.5 Hz, 1H), 0.05 (s, 9H); 13 C NMR (75 MHz, CDCl3): 144.6, 139.7, 136.3, 128.3, (2C), 116.5, 103.0, 65.6, 50.9, 35.9, -0.4 (3C); IR (ATR): νmax 2955, 1640, 1466, 1435, 1250, 1094, 870, 840, 749 cm -1 ; APCIHRMS m/z calcd for C14H22IOSi [M+H] , found S22

23 1-tert-Butoxycarbonyl-2-methylpyrrole. To a solution of pyrole-2-carboxylic acid (3.0 g, 27.0 mmol) in THF at 0 C was added LiAlH4 (4.1 g, mmol) portionwise. The resulting mixture was heated under reflux overnight. The reaction mixture was then cooled down to 0 C and diluted with Et2O, water was carefully added, followed by a 1M aq. solution of NaOH. The resulting solution was stirred for several minutes and the insolubles were filtered off over a pad of Celite. The filtrate was then extracted twice with Et2O, the organic layers were combined, washed with brine and dried over Na2SO4. Carefull evaporation (400 mbar) of the solvent allowed to afford 2-methylpyrrole which was directly used in the next step without further purification. To a solution of 2-methylpyrrole in MeCN was added di-tert-butyl dicarbonate (7.1 g, 32.4 mmol) and DMAP (330 mg, 2.7 mmol) at room temperature and the resulting mixture was stirred at room temperature overnight. The reaction mixture was then diluted in Et2O and washed successively with a satd. aq. solution of NaHCO3, a 1M aq. solution of HCl and brine, then dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was the purified by flash column chromatography over silica gel (Petroleum ether/ EtOAc : 100/0 to 95/5) to afford 1-tert-butoxycarbonyl-2-methylpyrrole (3.96 g, 21.9 mmol, 81%) as a colorless oil. This compound has been previously reported. S24 S23

24 Experimental Procedures and Characterization Data: Copper-Catalyzed Photoredox Reduction of Aryl Halides General procedure: An oven-dried vial was charged with [(DPEphos)(bcp)Cu]PF6 (11 mg, 0.01 mmol) and the corresponding aryl halide 1 (0.20 mmol). The vial was evacuated under high vacuum, backfilled with argon and sealed with a rubber septum. Acetonitrile (2 ml) and ipr2net (350 µl, 2.00 mmol) were next added and the reaction mixture was stirred under blue LEDs irradiation for 16 h. The mixture was filtered through a pad of Celite (rinsed with Et2O) and concentrated under reduced pressure. The yield of 2 was determined by 1 H NMR analysis with p-anisaldehyde (24 µl, 0.20 mmol) as internal standard. Representative example on a 1 mmol scale: An oven-dried vial was charged with [(DPEphos)(bcp)Cu]PF6 (55 mg, 0.05 mmol) and 4-iodobiphenyl 1a (280 mg, 1.00 mmol). The vial was evacuated under high vacuum, backfilled with argon and sealed with a rubber septum. Acetonitrile (10 ml) and ipr2net (1.74 ml, mmol) were next added and the reaction mixture was stirred under blue LEDs irradiation for 68 h. The mixture was filtered through a pad of Celite (rinsed with Et2O) and concentrated under reduced pressure. The residue was then purified by flash chromatography over silica gel (Petroleum ether) to afford biphenyl 2a (143 mg, 0.93 mmol, 93%) as a white solid. The spectroscopic data were found identical to those of a commercial sample of biphenyl. S24

25 Experimental Procedures and Characterization Data: Copper-Catalyzed Photoredox Cyclization of Aryl Iodides General procedure: An oven-dried vial was charged with [(DPEphos)(bcp)Cu]PF6 (22 mg, 0.02 mmol) and the corresponding aryl iodide 3 (0.20 mmol). The vial was evacuated under high vacuum, backfilled with argon and sealed with a rubber septum. Acetonitrile (2 ml) and ipr2net (350 µl, 2.00 mmol) were next added and the reaction mixture was stirred in a photoreactor under 420 nm wavelength irradiation for 16 h. The mixture was filtered through a pad of Celite (rinsed with Et2O) and concentrated under reduced pressure. The residue was then purified by flash chromatography over silica gel to afford the corresponding pure product 4. 1-Acetyl-3-methylindoline 4a. Yield: 71% (25 mg, 0.14 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 80/20; White solid. This compound has been previously reported. S16 1-tert-Butoxycarbonyl-3-methylindoline 4b. Yield: 64% (30 mg, 0.13 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 80/20; Pale yellow solid. This compound has been previously reported. S25 S25

26 1,3-Dimethylindoline 4c. Yield: 85% (25 mg, 0.17 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 100/0 to 97/3; Pale yellow volatile liquid. This compound has been previously reported. S26 1-Acetyl-5-methoxycarbonyl-3-methylindoline 4d. Yield: 67% (31 mg, 0.13 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 80/20 to 70/30; Pale yellow paste; 1 H NMR (300 MHz, CDCl3): 8.21 (d, J = 8.6 Hz, 1H), 7.92 (dd, J = 8.6 and 1.6 Hz, 1H), 7,84 (s, 1H), 4.27 (A of ABX syst., J = 9.6 and 9.6 Hz, 1H), 3.90 (s, 3H), 3.75 (B of ABX syst., J = 10.0 and 6.8 Hz, 1H), 3.53 (m, 1H), 2.25 (s, 3H), 1.39 (d, J = 6.9 Hz, 3H); 13 C NMR (75 MHz, CDCl3): 169.3, 167.0, 146.5, 136.6, 130.5, 125.5, 125.1, 116.3, 57.5, 52.1, 34.6, 24.4, 20.4; IR (ATR): νmax 2954, 1712, 1671, 1394, 1257, 770 cm -1 ; ESIHRMS m/z calcd for C13H15NNaO3 [M+Na] , found Acetyl-5-cyano-3-methylindoline 4e. Yield: 67% (27 mg, 0.13 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 80/20 to 60/40; Off-white solid. This compound has been previously reported. S27 S26

27 1-Acetyl-6-fluoro-3-methylindoline 4f. Yield: 65% (25 mg, 0.13 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 70/30; Pale yellow oil; 1 H NMR (300 MHz, CDCl3): 7.92 (dd, J = 10.6 and 2.4 Hz, 1H), 7.04 (dd, J = 8.2 and 5.5 Hz, 1H), 6.69 (d, J = 8.5 and 2.4 Hz, 1H), 4.22 (A of ABX syst., J = 9.7 and 9.7 Hz, 1H), 3.59 (B of ABX syst., J = 10.1 and 6.5 Hz, 1H), 3.45 (m, 1H), 2.20 (s, 3H), 1.32 (d, J = 6.9 Hz, 3H); 13 C NMR (75 MHz, CDCl3): 169.0, (d, J = Hz), (d, J = 12.5 Hz), 131.8, (d, J = 10.3 Hz), (d, J = 23.3 Hz), (d, J = 28.5 Hz), 57.7, 34.3, 24.2, 20.6; 19 F NMR (377 MHz, CDCl3): (ddd, J = 10.7, 8.9 and 5.6 Hz); IR (ATR): νmax 2965, 1650, 1493, 1439, 1409, 862, 732 cm -1 ; ESIHRMS m/z calcd for C11H13FNO [M+H] , found Acetyl-6-methoxy-3-methylindoline 4g. Yield: 66% (27 mg, 0.13 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 90/10 to 80/20; Brown solid; Mp: 66 C; 1 H NMR (300 MHz, CDCl3): 7.87 (d, J = 2.4 Hz, 1H), 7.02 (d, J = 8.1 Hz, 1H), 6.58 (d, J = 8.1 and 2.4 Hz, 1H), 4.20 (A of ABX syst., J = 9.6 and 9.6 Hz, 1H), 3.80 (s, 3H), 3.57 (B of ABX syst., J = 10.0 and 6.5 Hz, 1H), 3.42 (m, 1H), 2.20 (s, 3H), 1.31 (d, J = 6.7 Hz, 3H); 13 C NMR (75 MHz, CDCl3): 168.8, 159.7, 143.6, 128.5, 123.7, 110.1, 102.9, 57.8, 55.7, 34.2, 24.4, 20.7; IR (ATR): νmax 2963, 1659, 1599, 1489, 1399, 1031, 866 cm -1 ; ESIHRMS m/z calcd for C12H16NO2 [M+H] , found S27

28 Methyl 1-acetylindoline-3-acetate 4h. Following the general procedure under blue LEDs irradiation. Yield: 43% (20 mg, 0.09 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 60/40; Pale yellow solid; Mp: 41 C; 1 H NMR (300 MHz, CDCl3): 8.21 (d, J = 8.1 Hz, 1H), 7.23 (t, J = 8.1 Hz, 1H), 7.15 (d, J = 7.4 Hz, 1H), 7.03 (td, J = 7.5 and 1.0 Hz, 1H), 4.32 (A of ABX syst., J = 10.2 and 9.1 Hz, 1H), 3.83 (obs. m, 1H), 3.75 (obs. B of ABX syst., 1H), 3.73 (obs. s, 3H), 2.85 (A of A B X syst., J = 16.6 and 4.4 Hz, 1H), 2.56 (B of A B X syst., J = 16.6 and 9.8 Hz, 1H), 2.23 (s, 3H); 13 C NMR (75 MHz, CDCl3): 172.4, 168.8, 142.8, 133.1, 128.6, 123.9, 123.7, 117.3, 55.3, 52.1, 39.8, 36.7, 24.4; IR (ATR): νmax 2953, 1735, 1653, 1483, 1406, 1201, 1170, 762 cm -1 ; ESIHRMS m/z calcd for C13H15NNaO3 [M+H] , found Methyl-2,3-dihydrobenzofuran 4i. Yield: 60%. This compound is volatile. After concentration under reduced pressure (400 mbar), p-anisaldehyde (1 equiv. 24 µl, 0.20 mmol) was added and the yield was determined by 1 H NMR analysis. This compound has been previously reported. S28 S28

29 5-Acetyl-3-methyl-2,3-dihydrobenzofuran 4j. Yield: 74% (26 mg, 0.15 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 95/5 to 90/10; Pale yellow oil; 1 H NMR (300 MHz, CDCl3): (m, 2H), 6.79 (d, J = 8.4 Hz, 1H), 4.77 (A of ABX syst., J = 9.0 and 9.0 Hz, 1H), 4.16 (B of ABX syst., J = 9.0 and 7.3 Hz, 1H), 3.56 (m, 1H), 2.54 (s, 3H), 1.35 (d, J = 6.9 Hz, 3H); 13 C NMR (75 MHz, CDCl3): 196.8, 164.2, 133.2, 130.9, 130.6, 124.6, 109.2, 79.7, 36.0, 26.5, 19.5; IR (ATR): νmax 2963, 1673, 1606, 1251, 1118, 957, 822 cm -1 ; ESIHRMS m/z calcd for C11H13O2 [M+H] , found Methyl 3-methyl-2,3-dihydrobenzofuran-5-carboxylate 4k. Yield: 56% (21 mg, 0.11 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 95/5 to 90/10; Pale yellow oil; 1 H NMR (300 MHz, CDCl3): (m, 2H), 6.78 (d, J = 8.4 Hz, 1H), 4.76 (A of ABX syst., J = 8.9 and 8.9 Hz, 1H), 4.15 (B of ABX syst., J = 8.8 and 7.4 Hz, 1H), 3.88 (s, 3H), 3.56 (m, 1H), 1.35 (d, J = 6.8 Hz, 3H); 13 C NMR (75 MHz, CDCl3): 167.1, 164.0, 132.8, 131.2, 125.9, 122.9, 109.3, 79.6, 52.0, 36.1, 19.5; IR (ATR): νmax 2963, 1713, 1611, 1265, 960, 772 cm -1 ; ESIHRMS m/z calcd for C11H13O3 [M+H] , found Cyano-3-methyl-2,3-dihydrobenzofuran 4l. Yield: 72% (23 mg, 0.14 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 95/5 to 90/10; Pale yellow solid. This compound has been previously reported. S29 S29

30 1,1-Dimethoxycarbonyl-3-methylindane 4m. Yield: 50% (25 mg, 0.10 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 95/5 to 90/10; Pale yellow solid; Mp: 26 C; 1 H NMR (300 MHz, CDCl3): 7.54 (dd, J = 7.4 and 1.4 Hz, 1H), 7.32 (obs. td, J = 7.4 and 1.4 Hz, 1H), (obs. m, 2H), 3.79 (s, 3H), 3.71 (s, 3H), 3.37 (m, 1H), 3.03 (A of ABX syst., J = 13.1 and 7.6 Hz, 1H), 2.16 (B of ABX syst., J = 13.2 and 8.7 Hz, 1H), 1.34 (d, J = 6.9 Hz, 3H); 13 C NMR (75 MHz, CDCl3): 171.5, 171.1, 148.8, 138.9, 128.9, 126.9, 126.6, 123.5, 64.7, 53.0 (2C), 43.2, 37.5, 19.7; IR (ATR): νmax 2956, 1732, 1434, 1259, 1231, 1109, 759 cm -1 ; ESIHRMS m/z calcd for C14H16NNaO4 [M+Na] , found ',2',3-Trimethyl-2,3-dihydrospiro{indene-1,5'-[1,3]dioxane} 4n. Yield: 54% (25 mg, 0.11 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 98/2; Pale yellow oil; 1 H NMR (300 MHz, CDCl3): (m, 1H), (m, 3H), 4.18 (d, J = 11.2 Hz, 1H), 3.83 (d, J = 11.2 Hz, 1H), 3.75 (dd, J = 11.2 and 1.6 Hz, 1H), 3.68 (dd, J = 11.2 and 1.6 Hz, 1H), 3.25 (app. sext, J = 7.3 Hz, 1H), 2.61 (A of ABX syst., J = 13.1 and 7.8 Hz, 1H), 1.58 (obs. B of ABX syst., 1H), 1.58 (s, 3H), 1.51 (s, 3H), 1.33 (d, J = 6.9 Hz, 3H); 13 C NMR (75 MHz, CDCl3): 149.1, 144.7, 127.9, 126.7, 123.9, 123.8, 98.0, 69.6, 68.0, 46.4, 43.5, 36.4, 26.2, 21.8, 20.5; IR (ATR): νmax 2956, 2859, 1382, 1196, 1090, 832, 753 cm -1 ; ESIHRMS m/z calcd for C15H21O2 [M+H] , found S30

31 1-Methoxycarbonyl-3-methylindane 4o. cis/trans = 3:2 (determined by 1 H NMR analysis of the purified mixture of isomers). Yield: 53% (20 mg, 0.11 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 90/10; Pale yellow oil. This compound has been previously reported. S30 3-Methyl-1-(trimethylsilyloxymethyl)indane 4p. cis/trans = 5:4 (determined by 1 H NMR analysis of the purified mixture of isomers). Yield: 51% (24 mg, 0.10 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 100/0 to 97/3; Pale yellow oil; 1 H NMR (300 MHz, CDCl3): (m, 4H), 3.96 (A of ABX syst., J = 9.8 and 6.3 Hz, 0.55H, cis isomer), 3.71 (obs. A of ABX syst., J = 9.8 and 6.1 Hz, 0.45H, trans isomer), 3.66 (obs. B of ABX syst., J = 9.8 and 7.4 Hz, 0.55H, cis isomer), 3.55 (B of ABX syst., J = 9.8 and 8.1 Hz, 0.45H, trans isomer), (m, 2H), 2.50 (A of A B X Y syst., J = 12.6, 7.6 and 7.6 Hz, 0.55H, cis isomer), 2.20 (A of A B X Y syst., J = 12.8, 7.8 and 3.5 Hz, 0.45H, trans isomer), 1.80 (B of A B X Y syst., J = 12.9, 7.8 and 7.8 Hz, 0.45H, trans isomer), 1.34 and 1.29 (obs. d, J = 6.8 Hz, 3H, cis and trans isomers), (obs. B of A B X Y syst., 0.55H, cis isomer), 0.16 (s, 4.95H, cis isomer), 0.11 (s, 4.05H, cis isomer); 13 C NMR (75 MHz, CDCl3): 149.2, 149.2, 144.7, 144.2, 127.1, 126.9, (2C), 124.8, 124.1, 123.5, 123.3, 67.1, 66.2, 46.5, 46.4, 39.2, 38.2, 37.9, 37.6, 20.5, 20.3, -0.3 (3C), -0.4 (3C); IR (ATR): νmax 2956, 1250, 1083, 875, 840, 751 cm -1 ; ESIHRMS m/z calcd for C11H13 [M- OTMS] , found S31

32 Experimental Procedures and Characterization Data: Copper-Catalyzed Photoredox Transformations of Alkyl Halides General procedure: An oven-dried vial was charged with [(DPEphos)(bcp)Cu]PF6 (5 or 10 mol%) and the corresponding alkyl halide 5, 7, 9 or 11 (1 equiv.). The vial was evacuated under high vacuum, backfilled with argon and sealed with a rubber septum. Acetonitrile (0.1 M) and ipr2net (5 or 10 equiv.) were next added and the reaction mixture was stirred in a photoreactor under 420 nm wavelength irradiation for 16 h. The mixture was filtered through a pad of Celite (rinsed with Et2O) and concentrated under reduced pressure. The residue was then purified by flash chromatography over silica gel to afford the corresponding pure product 6, 8, 10 or Methoxy-1,3,5(10)-estatriene 6. Following the general procedure from 5 (104 mg, 0.26 mmol) with 10 equiv. of ipr2net (450 µl, 2.60 mmol) under blue LEDs irradiation. Yield: 78% (55 mg, 0.20 mmol). Solvent system for flash column chromatography: petroleum ether/dcm: 75/25; White solid. This compound has been previously reported. S31 Trans-p-menthane 8. Following the general procedure from 7 (44 mg, 0.20 mmol) with 10 equiv. of ipr2net (350 µl, 2.00 mmol) and during 60 h of irradiation. At the end of the reaction, the mixture was diluted with pentane and filtered through a pad of Celite (rinsed with pentane). The filtrate was washed twice with water, brine and dried over MgSO4. The solvent was carefully evaporated (20 C, 280 mbar) to afford trans-pmenthane 8 (24 mg, contaminated with 23% of pentane). Corrected yield: 74%. S32

33 Dimethyl 3-methylcyclopentane-1,1-dicarboxylate 10. Following the general procedure from 9 (65 mg, 0.20 mmol) with 5 equiv. of ipr2net (175 µl, 1.00 mmol). Yield: 63% (25 mg, 0.13 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 95/5; Colorless oil (slightly volatile). This compound has been previously reported. S15 3-Methyl-1-tosylpyrrolidine 12. Following the general procedure from 11 (64 mg, 0.20 mmol) with 5 equiv. of ipr2net (175 µl, 1.00 mmol). Yield: 56% (27 mg, 0.11 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 92/8; White solid. This compound has been previously reported. S28 S33

34 Experimental Procedures and Characterization Data: Copper-Catalyzed Photoredox Direct Arylation of (Hetero)arenes with Aryl Halides General procedure: An oven-dried vial was charged with [(DPEphos)(bcp)Cu]PF6 (22 mg, 0.02 mmol), Cy2NiBu (24 mg, 0.10 mmol), K2CO3 (55 mg, 0.40 mmol) and the corresponding arylhalide 1 (0.20 mmol). The vial was evacuated under high vacuum, backfilled with argon and sealed with a rubber septum. Acetonitrile (2 ml) and the corresponding (hetero)arenes 13 or 14 (4.00 mmol) were next added and the reaction mixture was stirred in a photoreactor under 420 nm wavelength irradiation for 2 to 5 days. The mixture was filtered through a pad of Celite (rinsed with Et2O) and concentrated under reduced pressure. The residue was then purified by flash chromatography over silica gel to afford the corresponding pure product 15 or 16. Note: in some cases, the product was found to be contaminated with residual Cy2NiBu which can be removed after the flash chromatography by an acidic work up using a 1M aq. solution of HCl. 2-[(1,1'-Biphenyl)-4-yl]-1-methylpyrrole 15a. Starting from the corresponding iodide. Yield: 66% (31 mg, 0.13 mmol). Solvent system for flash column chromatography: petroleum ether/dcm: 75/25; Off-white solid. This compound has been previously reported. S32 S34

35 2-[4-(Methoxycarbonyl)phenyl]-1-methylpyrrole 15b. Starting from the corresponding iodide. Yield: 74% (32 mg, 0.15 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 90/10; Beige solid. This compound has been previously reported. S33 2-(4-Cyanophenyl)-1-methylpyrrole 15c. Starting from the corresponding iodide. Yield: 75% (27 mg, 0.15 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 90/10; White solid. This compound has been previously reported. S34 1-Methyl-2-[4-(trifluoromethyl)phenyl]pyrrole 15d. Starting from the corresponding iodide. Yield: 69% (31 mg, 0.14 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 100/0 to 96/4; Colorless oil. This compound has been previously reported. S33 2-(4-Bromophenyl)-1-methylpyrrole 15e. Starting from the corresponding iodide. Yield: 72% (34 mg, 0.14 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 90/10; White solid. This compound has been previously reported. S33 S35

36 1-Methyl-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]pyrrole 15f. Starting from the corresponding iodide during 5 days. Yield: 53% (30 mg, 0.11 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 90/10; Brown solid. Mp : C, 1 HNMR (CDCl3, 300 MHz) 7.84 (d, J = 8.1 Hz, 2H), 7.42 (d, J = 8.1 Hz, 2H), 6.74 (m, 1H), 6.29 (m, 1H), 6.21 (m, 1H), 3.69 (s, 3H), 1.34 (s, 12H); 13 CNMR (CDCl3, 75 MHz) 136.1, (2C), 134.6, (2C), 124.4, 109.3, 108.1, 83.9 (2C), 35.3, 25.0 (4C); IR (ATR): νmax 2977, 1612, 1399, 1363, 1264, 1143, 1091, 860, 706, ESIHRMS m/z calcd for C17H23BNO2 [M+H] , found [4-(Methoxycarbonyl)-2-methylphenyl]-1-methylpyrrole 15g. Starting from the corresponding iodide. Yield: 59% (27 mg, 0.12 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 100/0 to 95/5; Pale yellow oil. 1 HNMR (300 MHz, CDCl3) 7.96 (s, 1H), 7.88 (d, J = 7.8 Hz, 1H), 7.30 (d, J = 7.8 Hz, 1H), 6.74 (dd, J = 2.7 and 1.6 Hz, 1H), 6.23 (dd, J = 3.9 and 2.7 Hz, 1H), 6.11 (dd, J = 3.3 and 1.6 Hz, 1H), 3.94 (s, 3H), 3.42 (s, 3H), 2.27 (s, 3H); 13 CNMR (75 MHz, CDCl3) 167.2, 138.4, 138.0, 132.2, 131.3, 131.2, 129.4, 126.7, 122.7, 109.3, 107.7, 52.2, 34.4, 20.3; IR (ATR): νmax 2950, 2930, 1720, 1610, 1435, 1258, 1196, 849, 771; ESIHRMS m/z calcd for C14H16NO2 [M+H] , found Methyl-2-(pyrid-3-yl)pyrrole 15h. Starting from the corresponding iodide. Yield: 54% (17 mg, 0.12 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 90/10 to 80/20; Pale yellow oil. This compound has been previously reported. S35 S36

37 1-Methyl-2-(thiophen-2-yl)pyrrole 15i. Starting from the corresponding iodide. Yield: 64% (21 mg, 0.13 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 100/0 to 98/2; Brownish oil. This compound has been previously reported. S36 3-Acetyl-2-[4-cyanophenyl]-1-methylpyrrole 15j. Starting from the corresponding iodide. Yield: 47% (21 mg, 0.09 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 90/10; White solid. This compound has been previously reported. S37 3-Acetyl-2-[4-(methoxycarbonyl)phenyl]-1-methylpyrrole 15k. Starting from the corresponding iodide. Yield: 58% (30 mg, 0.12 mmol). Solvent system for flash column chromatography: petroleum ether/etoac: 80/20 to 60/40; White solid. Mp: 91 C, 1 HNMR (300 MHz, CDCl3) 8.12 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.1 Hz, 2H), 6.66 (app. s, 2H), 3.94 (s, 3H), 3.41 (s, 3H), 2.16 (s, 3H); 13 CNMR (75 MHz, CDCl3) 193.7, 166.8, 137.0, 136.4, (2C), 130.3, (2C), 123.8, 122.8, 110.2, 52.4, 34.8, 28.8; IR (ATR): νmax 3126, 1709, 1658, 1610, 1487, 1431, 1360, 1179, 925, 870; ESIHRMS m/z calcd for C15H16NO3 [M+H] , found S37