Supporting Information For: Rhodium-Catalyzed Hydrofunctionalization: Enantioselective Coupling of Indolines and 1,3-Dienes

Supporting Information For: Rhodium-Catalyzed Hydrofunctionalization: Enantioselective Coupling of Indolines and 1,3-Dienes Xiao-Hui Yang and Vy M. Dong* dongv@uci.edu Department of Chemistry, University of California, Irvine, California 92697-2025, United States Table of Contents 1. General...S1 2. Typical procedures for the hydrofunctionalization of 1,3-dienes...S2 3. Typical procedures for the hydroamination of 1,3-dienes...S3 4. Synthesis of N-allylic indole 5...S9 5. References...S10 6. NMR spectra...s11-36 7. SFC spectra...s37-60 1. General: Commercial reagents were purchased from Sigma Aldrich, Strem, Alfa Aesar, Acros Organics or TCI and used without further purification. 1,2-Dichloroethane and tetrahydrofuran were purified using an Innovative Technologies Pure Solv system, degassed by three freeze-pump-thaw cycles, and stored over 3A MS within a N 2 filled glove box. All experiments were performed in oven-dried or flame-dried glassware. Reactions were monitored using either thin-layer chromatography (TLC) or gas chromatography using an Agilent Technologies 7890A GC system equipped with an Agilent Technologies 5975C inert XL EI/CI MSD. Visualization of the developed plates was performed under UV light (254 nm) or KMnO 4 stain. Organic solutions were concentrated under reduced pressure on a Büchi rotary evaporator. Column chromatography was performed with Silicycle Silia-P Flash Silica Gel using glass columns. Solvents were purchased from Fisher. 1 H and 13 C NMR spectra were recorded on Bruker CRYO500 or DRX400 spectrometer. 1 H NMR spectra were internally referenced to the residual solvent signal or TMS. 13 C NMR spectra were internally referenced to the residual solvent signal. Data for 1 H NMR are reported as follows: chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet), coupling constant (Hz), integration. Data for 13 C NMR are reported in terms of chemical shift (δ ppm). Infrared (IR) spectra were obtained on a Nicolet is5 FT-IR spectrometer with an id5 ATR, and are reported in terms of frequency of absorption (cm -1 ). High resolution mass spectra (HRMS) were obtained on a micromass 70S-250 spectrometer (EI) or an ABI/Sciex QStar Mass Spectrometer (ESI). Enantiomeric excesses for enantioselective reactions were determined by chiral SFC analysis using an Agilent Technologies HPLC (1200 series) system and Aurora A5 Fusion. 1,3-Dienes used here were known compounds and synthesized according to the reported methods. 1 S1

2. Typical procedures for the hydrofunctionalization of 1,3-dienes A mixture of [Rh(COD)Cl] 2 (2.0 mg, 0.004 mmol), ligand (0.008 mmol), acid (0.1 mmol), nucleophile (0.20 mmol), 1,3-diene (0.30 mmol), and DCE (0.4 ml) were added to a 1 dram vial in the glove box. After heating the reaction mixture for 24 h, the resulting solution was cooled to rt. The selectivity was determined by 1 H NMR analysis of the reaction prior to purification. The product was purified by column chromatography on silica gel using hexanes/etoac (15:1). (E)-2-(4-(4-methoxyphenyl)but-3-en-2-yl)-1,3-diphenylpropane-1,3-dione Colorless oil, 51% yield 1 H NMR (500 MHz, CDCl 3) δ 8.03 7.99 (m, 2H), 7.96 7.92 (m, 2H), 7.57 7.50 (m, 2H), 7.46 7.38 (m, 4H), 7.08 7.04 (m, 2H), 6.77 6.72 (m, 2H), 6.31 (d, J = 16.0 Hz, 1H), 5.97 (dd, J = 16.0, 8.5 Hz, 1H), 5.31 (d, J = 9.0 Hz, 1H), 3.76 (s, 3H), 3.64 3.55 (m, 1H), 1.21 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 195.30, 195.09, 159.04, 137.19, 137.14, 133.63, 133.40, 130.30, 130.06, 130.02, 128.99, 128.92, 128.86, 128.82, 127.40, 113.90, 63.41, 55.39, 38.75, 19.17. IR (ATR): 2961, 2835, 1694, 1510, 1447, 1246, 1175, 1030, 969, 688 cm -1. HRMS calculated for C 26H 25O 3 [M+H] + 385.1799, found 385.1800. (E)-1-methoxy-4-(3-(3-phenylpropoxy)but-1-en-1-yl)benzene Colorless oil, 37% yield. 1 H NMR (500 MHz, CDCl 3) δ 7.34 7.29 (m, 2H), 7.28 7.24 (m, 2H), 7.21 7.15 (m, 3H), 6.89 6.83 (m, 2H), 6.44 (d, J = 16.0 Hz, 1H), 5.98 (dd, J = 16.0, 7.5 Hz, 1H), 4.00 3.91 (m, 1H), 3.81 (s, 3H), 3.52 (dt, J = 9.5, 6.5 Hz, 1H), 3.36 (dt, J = 9.5, 6.5 Hz, 1H), 2.76 2.62 (m, 2H), 1.94 1.87 (m, 2H), 1.33 (d, J = 6.5 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 159.21, 142.10, 130.34, 129.89, 129.51, 128.48, 128.25, 127.59, 125.68, 113.97, 76.64, 67.35, 55.30, 32.40, 31.48, 21.75. IR (ATR): 2930, 1607, 1509, 1453, 1245, 1174, 1033, 829, 744, 698 cm -1. HRMS calculated for C 20H 25O 2 [M+H] + 297.1850, found 297.1852. (E)-(4-(4-methoxyphenyl)but-3-en-2-yl)(4-tolyl)sulfane Colorless oil, 61% yield. 1 H NMR (500 MHz, CDCl 3) δ 7.36 7.30 (m, 2H), 7.25 7.20 (m, 2H), 7.11 7.06 (m, 2H), 6.86 6.80 (m, 2H), 6.16 (d, J = 16.0 Hz, 1H), 6.03 (dd, J = 16.0, 8.0 Hz, 1H), 3.85 3.77 (m, 4H), 2.31 (s, 3H), 1.45 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 159.21, 137.61, 134.03, 130.95, 129.88, 129.80, 129.59, 129.40, 127.58, 114.05, 55.42, 47.04, 21.26, 20.84. IR (ATR): 2922, 1607, 1510, 1491, 1245, 1174, 1033, 962, 908, 807, 731 cm -1. HRMS calculated for C 18H 21OS [M+H] + 285.1308, found 285.1310. S2

3. Typical procedures for the hydroamination of 1,3-dienes A mixture of [Rh(COD)OMe] 2 (1.9 mg, 0.004 mmol), JoSPOphos (4.0 mg, 0.008 mmol), triphenylacetic acid (14.4 mg, 0.1 mmol), amine 1 (0.20 mmol), 1,3-diene 2 (0.30 mmol), and DCE (0.4 ml) were added to a 1 dram vial in the glove box. After heating the reaction mixture at 60 o C for 24 h, the resulting solution was cooled to rt. The selectivity was determined by 1 H NMR analysis of the reaction prior to purification. The product 3 was purified by column chromatography on silica gel using hexanes/etoac (15:1). (R, E)-4-chloro-1-(4-phenylbut-3-en-2-yl)indoline (3aa) 2 Colorless oil, 81% yield, 96% ee, [ ] 24 D = -121.2 (c 1.0, CH 2Cl 2). 1 H NMR (400 MHz, CD 2Cl 2) δ 7.40 7.35 (m, 2H), 7.34 7.26 (m, 2H), 7.24 7.17 (m, 1H), 7.09 6.96 (m, 2H), 6.63 6.55 (m, 2H), 6.51 (d, J = 8.0 Hz, 1H), 6.33 (dd, J = 16.0, 6.0 Hz, 1H), 4.41 4.32 (m, 1H), 3.49 3.34 (m, 2H), 2.94 (t, J = 8.4 Hz, 2H), 1.41 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl 3) δ 151.62, 137.49, 131.03, 130.85, 130.76, 128.91, 127.77, 127.46, 126.64, 124.75, 117.46, 107.94, 52.79, 47.65, 28.59, 16.51. Chiral SFC: 250 mm CHIRALCEL IC, 3% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 3.5 min, t R2 (major) = 3.9 min. (R, E)-4-chloro-1-(4-phenylbut-3-en-2-yl)indoline (3ab) Colorless oil, 87% yield, 96% ee, [ ] 24 D = -56.2 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.40 7.35 (m, 2H), 7.33 7.27 (m, 2H), 7.26 7.19 (m, 1H), 7.00 6.93 (m, 1H), 6.60 6.52 (m, 2H), 6.39 (d, J = 8.0 Hz, 1H), 6.29 (dd, J = 16.0, 6.0 Hz, 1H), 4.39 4.28 (m, 1H), 3.57 3.43 (m, 2H), 3.03 2.93 (m, 2H), 1.41 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 152.95, 137.32, 131.32, 130.69, 130.05, 129.16, 128.94, 128.66, 127.91, 126.67, 117.23, 106.04, 53.03, 47.18, 27.85, 16.61. IR (ATR): 2925, 2848, 1598, 1453, 1263, 1159, 966, 749 cm -1. HRMS calculated for C 18H 19ClN [M+H] + 284.1201, found 284.1204. Chiral SFC: 250 mm CHIRALCEL IC, 4% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 5.2 min, t R2 (major) = 5.5 min. (R, E)-4-methyl-1-(4-phenylbut-3-en-2-yl)indoline (3ac) Colorless oil, 80% yield, 96% ee, [ ] 24 D = -95.2 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.39 7.34 (m, 2H), 7.32 7.27 (m, 2H), 7.24 7.18 (m, 1H), 6.93 (t, J = 7.5 Hz, 1H), 6.57 (dd, J = 16.0, 1.0 Hz, 1H), 6.44 (d, J = 7.5 Hz, 1H), 6.39 6.29 (m, 2H), 4.40 4.30 (m, 1H), 3.52 3.37 (m, 2H), 2.92 2.82 (m, 2H), 2.18 (s, 3H), 1.40 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 151.30, 137.48, 134.21, 130.96, 130.80, 129.31, 128.88, 127.73, 127.53, 126.60, 118.90, 105.57, 52.86, 47.36, 27.24, 18.65, 16.46. IR (ATR): 2970, 2842, 1593, 1461, 1260, 1158, 967, 749, 735 cm -1. HRMS calculated for C 19H 22N [M+H] + 264.1747, found 264.1748. Chiral SFC: S3

250 mm CHIRALCEL IC, 10% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 3.1 min, t R2 (major) = 3.5 min. (R, E)-4-methoxy-1-(4-phenylbut-3-en-2-yl)indoline (3ad) Colorless oil, 80% yield, 97% ee, [ ] 24 D = -58.4 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.40 7.34 (m, 2H), 7.33 7.27 (m, 2H), 7.24 7.19 (m, 1H), 7.00 (t, J = 8.0 Hz, 1H), 6.55 (dd, J = 16.0, 1.0 Hz, 1H), 6.32 (dd, J = 16.0, 6.0 Hz, 1H), 6.27 6.19 (m, 2H), 4.39 4.31 (m, 1H), 3.79 (s, 3H), 3.52 3.37 (m, 2H), 2.96 2.80 (m, 2H), 1.39 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 156.67, 153.29, 137.46, 130.95, 130.76, 128.88, 128.85, 127.74, 126.61, 116.49, 102.02, 101.08, 55.51, 52.92, 47.74, 25.51, 16.58. IR (ATR): 2970, 2835, 1612, 1464, 1255, 1160, 1086, 967, 749 cm -1. HRMS calculated for C 19H 22NO [M+H] + 280.1696, found 280.1698. Chiral SFC: 250 mm CHIRALCEL IC, 10% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 4.2 min, t R2 (major) = 4.9 min. (R, E)-5-fluoro-1-(4-phenylbut-3-en-2-yl)indoline (3ae) Colorless oil, 82% yield, 99% ee, [ ] 24 D = -115.0 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.39 7.35 (m, 2H), 7.33 7.27 (m, 2H), 7.26 7.19 (m 1H), 6.84 6.77 (m, 1H), 6.76 6.69 (m, 1H), 6.57 (dd, J = 16.0, 1.0 Hz, 1H), 6.42 (dd, J = 8.5, 4.5 Hz, 1H), 6.31 (dd, J = 16.0, 6.0 Hz, 1H), 4.33 4.24 (m, 1H), 3.48 3.38 (m, 2H), 2.93 (t, J = 8.5 Hz, 2H), 1.40 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 156.52 (d, J = 232.5 Hz), 147.91, 137.43, 132.67 (d, J = 7.5 Hz), 131.28, 130.48, 128.93, 127.85, 126.65, 113.00 (d, J = 22.5 Hz), 112.36 (d, J = 23.8 Hz), 108.02 (d, J = 8.8 Hz), 53.41, 48.22, 28.72 (d, J = 2.5 Hz), 16.50. IR (ATR): 2970, 2843, 1605, 1486, 1229, 1184, 966, 745 cm -1. HRMS calculated for C 18H 19FN [M+H] + 268.1497, found 268.1499. Chiral SFC: 250 mm CHIRALCEL IC, 7% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 2.7 min, t R2 (major) = 3.0 min. (R, E)-5-chloro-1-(4-phenylbut-3-en-2-yl)indoline (3af) Colorless oil, 80% yield, 94% ee, [ ] 24 D = -146.4 (c 1.0, CH 2Cl 2). 1 H NMR (400 MHz, CD 2Cl 2) δ 7.39 7.33 (m, 2H), 7.33 7.27 (m, 2H), 7.25 7.18 (m, 1H), 7.01 6.94 (m, 2H), 6.56 (dd, J = 16.0, 1.2 Hz, 1H), 6.42 (d, J = 8.4 Hz, 1H), 6.28 (dd, J = 16.0, 6.0 Hz, 1H), 4.35 4.26 (m, 1H), 3.52 3.37 (m, 2H), 2.93 (t, J = 8.4 Hz, 2H), 1.40 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl 3) δ 150.39, 137.34, 132.90, 131.28, 130.17, 128.93, 127.88, 127.08, 126.65, 124.88, 121.60, 108.49, 52.99, 47.87, 28.42, 16.56. IR (ATR): 2969, 2841, 1601, 1586, 1254, 1179, 966, 751 cm -1. HRMS calculated for C 18H 19ClN [M+H] + 284.1201, found 284.1201. Chiral SFC: 250 mm CHIRALCEL IC, 4% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 6.6 min, t R2 (major) = 7.2 min. (R, E)-5-bromo-1-(4-phenylbut-3-en-2-yl)indoline (3ag) S4

Colorless oil, 86% yield, 99% ee, [ ] 24 D = -176.6 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CDCl 3) δ 7.41 7.33 (m, 2H), 7.33 7.28 (m, 2H), 7.26 7.18 (m, 1H), 7.15 7.07 (m, 2H), 6.56 (dd, J = 16.0, 1.5 Hz, 1H), 6.44 6.37 (m, 1H), 6.28 (dd, J = 16.0, 6.0 Hz, 1H), 4.35 4.27 (m, 1H), 3.52 3.39 (m, 2H), 2.95 (t, J = 8.5 Hz, 2H), 1.40 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 150.80, 137.33, 133.40, 131.31, 130.11, 130.01, 128.93, 127.89, 127.65, 126.66, 109.12, 108.60, 52.92, 47.79, 28.36, 16.56. IR (ATR): 2922, 2851, 1595, 1465, 1259, 1162, 966, 737, 751 cm -1. HRMS calculated for C 18H 19BrN [M+H] + 328.0696, found 328.0701. Chiral SFC: 250 mm CHIRALCEL IC, 7% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 5.4 min, t R2 (major) = 6.0 min. (R, E)-5-methoxy-1-(4-phenylbut-3-en-2-yl)indoline (3ah) Colorless oil, 81% yield, 88% ee, [ ] 24 D = -118.0 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.40 7.34 (m, 2H), 7.32 7.27 (m, 2H), 7.23 7.19 (m, 1H), 6.73 6.69 (m, 1H), 6.62 6.53 (m, 2H), 6.45 (d, J = 8.5 Hz, 1H), 6.33 (dd, J = 16.0, 6.0 Hz, 1H), 4.30 4.23 (m, 1H), 3.70 (s, 3H), 3.42 3.31 (m, 2H), 2.90 (t, J = 8.5 Hz, 2H), 1.38 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 152.97, 145.85, 137.55, 132.50, 131.05, 131.02, 128.90, 127.74, 126.62, 112.29, 111.87, 108.54, 56.21, 53.19, 48.23, 28.99, 16.51. IR (ATR): 2932, 2828, 1593, 1488, 1234, 1139, 1034, 967, 745 cm -1. HRMS calculated for C 19H 22NO [M+H] + 280.1696, found 280.1694. Chiral SFC: 250 mm CHIRALCEL IC, 5% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 5.8 min, t R2 (major) = 6.9 min. (R, E)-6-methyl-1-(4-phenylbut-3-en-2-yl)indoline (3ai) Colorless oil, 89% yield, 94% ee, [ ] 24 D = -310.4 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.42 7.35 (m, 2H), 7.34 7.27 (m, 2H), 7.25 7.19 (m, 1H), 6.92 (d, J = 7.5 Hz, 1H), 6.57 (dd, J = 16.0, 1.0 Hz, 1H), 6.45 6.39 (m, 1H), 6.38 6.28 (m, 2H), 4.42 4.31 (m, 1H), 3.47 3.32 (m, 2H), 2.88 (t, J = 8.5 Hz, 2H), 2.26 (s, 3H), 1.40 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 151.76, 137.53, 137.22, 130.92, 130.86, 128.89, 127.86, 127.73, 126.63, 124.37, 118.07, 108.82, 52.54, 47.73, 28.21, 21.86, 16.34. IR (ATR): 2970, 2845, 1610, 1493, 1209, 1172, 1034, 967, 748 cm -1. HRMS calculated for C 19H 22N [M+H] + 264.1747, found 264.1746. Chiral SFC: 250 mm CHIRALCEL IC, 5% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 3.2 min, t R2 (major) = 3.9 min. (R, E)-6-methoxy-1-(4-phenylbut-3-en-2-yl)indoline (3aj) Colorless oil, 88% yield, 98% ee, [ ] 24 D = -239.2 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.41 7.35 (m, 2H), 7.33 7.27 (m, 2H), 7.25 7.19 (m, 1H), 6.91 (d, J = 8.0 Hz, 1H), 6.57 (d, J = 16.0 Hz, 1H), 6.32 (dd, J = 16.0, 6.0 Hz, 1H), 6.18 6.06 (m, 2H), 4.41 4.28 (m, 1H), 3.72 (s, 3H), 3.50 3.37 (m, 2H), 2.87 (t, J = 8.5 Hz, 2H), 1.40 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 160.41, 152.87, 137.43, 131.02, 130.59, 128.89, 127.77, 126.62, 124.64, 123.15, 101.23, 95.51, 55.59, 52.68, 48.16, 27.73, 16.46. IR (ATR): 2935, 2832, 1618, 1493, 1209, 1172, 1034, 967, 748 cm -1. HRMS calculated for C 19H 22NO [M+H] + 280.1696, found 280.1698. Chiral S5

SFC: 250 mm CHIRALCEL IC, 10% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 5.2 min, t R2 (major) = 7.3 min. (R, E)-1-(4-(4-fluorophenyl)but-3-en-2-yl)indoline (3ba) Colorless oil, 83% yield, 98% ee, [ ] 24 D = -124.8 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.43 7.34 (m, 2H), 7.11 6.99 (m, 4H), 6.65 6.50 (m, 3H), 6.28 (dd, J = 16.0, 6.0 Hz, 1H), 4.43 4.34 (m, 1H), 3.52 3.38 (m, 2H), 2.97 (t, J = 8.5 Hz, 2H), 1.43 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 162.56 (d, J = 243.8 Hz), 151.52, 133.73 (d, J = 3.8 Hz), 130.84, 130.52, 129.82, 128.17 (d, J = 7.6 Hz), 127.44, 124.75, 117.49, 115.67 (d, J = 21.3 Hz), 107.92, 52.74, 47.60, 28.56, 16.52. IR (ATR): 2972, 2843, 1604, 1507, 1485, 1225, 1157, 969, 744, 713 cm -1. HRMS calculated for C 18H 19FN [M+H] + 268.1497, found 268.1496. Chiral SFC: 250 mm CHIRALCEL IC, 7% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 3.1 min, t R2 (major) = 3.5 min. (R, E)-1-(4-(4-chlorophenyl)but-3-en-2-yl)indoline (3ca) Colorless oil, 82% yield, 94% ee, [ ] 24 D = -214.4 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.38 7.24 (m, 4H), 7.09 6.97 (m, 2H), 6.65 6.46 (m, 3H), 6.31 (dd, J = 16.0, 6.0 Hz, 1H), 4.40 4.31 (m, 1H), 3.50 3.34 (m, 2H), 2.94 (t, J = 8.5 Hz, 2H), 1.39 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 151.51, 136.07, 133.17, 131.59, 130.81, 129.77, 128.98, 127.92, 127.45, 124.76, 117.51, 107.87, 52.71, 47.62, 28.55, 16.46. IR (ATR): 2970, 2844, 1605, 1486, 1259, 1089, 1011, 968, 742, 713 cm -1. HRMS calculated for C 18H 19ClN [M+H] + 284.1201, found 284.1203. Chiral SFC: 250 mm CHIRALCEL IC, 10% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 3.5 min, t R2 (major) = 3.9 min. (R, E)-1-(4-(4-bromophenyl)but-3-en-2-yl)indoline (3da) Colorless oil, 85% yield, 93% ee, [ ] 24 D = -112.0 (c 1.0, CH 2Cl 2). 1 H NMR (400 MHz, CD 2Cl 2) δ 7.46 7.39 (m, 2H), 7.28 7.22 (m, 2H), 7.07 6.97 (m, 2H), 6.61 6.55 (m 1H), 6.54 6.47 (m, 2H), 6.33 (dd, J = 16.0, 5.6 Hz, 1H), 4.39 4.30 (m, 1H), 3.48 3.34 (m, 2H), 2.94 (t, J = 8.4 Hz, 2H), 1.40 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CD 2Cl 2) δ 151.51, 136.54, 131.96, 131.79, 130.83, 129.85, 128.27, 127.47, 124.79, 121.33, 117.54, 107.89, 52.75, 47.67, 28.58, 16.45. IR (ATR): 2970, 2842, 1605, 1484, 1255, 1071, 1007, 968, 742, 693 cm -1. HRMS calculated for C 18H 19BrN [M+H] + 328.0696, found 328.0698. Chiral SFC: 250 mm CHIRALCEL IC, 12% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 3.6 min, t R2 (major) = 4.0 min. (R, E)-1-(4-(4-tolyl)but-3-en-2-yl)indoline (3ea) Colorless oil, 81% yield, 98% ee, [ ] 24 D = -215.2 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.26 (d, J = 8.0 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H), 7.06 7.03 (m, 1H), 7.02 6.98 (m, 1H), 6.58 (td, J = 7.5, 1.0 Hz, 1H), 6.56 6.49 (m, 2H), 6.27 (dd, J = 16.0, 6.0 Hz, 1H), 4.39 4.30 (m, 1H), 3.47 3.36 (m, 2H), 2.93 (t, J = 8.5 Hz, 2H), 2.31 (s, 3H), 1.39 (d, J S6

= 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 151.63, 137.71, 134.65, 130.92, 130.86, 129.61, 129.57, 127.45, 126.52, 124.73, 117.43, 107.96, 52.84, 47.63, 28.59, 21.26, 16.54. IR (ATR): 2969, 2843, 1605, 1485, 1458, 1254, 1080, 969, 799, 743, 712 cm -1. HRMS calculated for C 19H 22N [M+H] + 264.1747, found 264.1748. Chiral SFC: 250 mm CHIRALCEL IC, 4% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 3.7 min, t R2 (major) = 4.1 min. (R, E)-1-(4-(4-methoxyphenyl)but-3-en-2-yl)indoline (3fa) Colorless oil, 80% yield, 96% ee, [ ] 24 D = -146.0 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.34 7.29 (m, 2H), 7.06 6.98 (m, 2H), 6.87 6.81 (m, 2H), 6.58 (td, J = 7.5, 1.0 Hz, 1H), 6.55 6.49 (m, 2H), 6.19 (dd, J = 16.0, 6.0 Hz, 1H), 4.38 4.30 (m, 1H), 3.79 (s, 3H), 3.47 3.37 (m, 2H), 2.94 (t, J = 8.5 Hz, 2H), 1.39 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 159.60, 151.68, 130.85, 130.46, 130.19, 128.41, 127.77, 127.45, 124.73, 117.37, 114.28, 107.93, 55.63, 52.82, 47.59, 28.59, 16.63. IR (ATR): 2969, 2834, 1605, 1509, 1486, 1246, 1173, 1032, 968, 737, 710 cm -1. HRMS calculated for C 19H 22NO [M+H] + 280.1696, found 280.1693. Chiral SFC: 250 mm CHIRALCEL IC, 3% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 13.5 min, t R2 (major) = 14.2 min. (R, E)-1-(4-(3-chlorophenyl)but-3-en-2-yl)indoline (3ga) Colorless oil, 78% yield, 97% ee, [ ] 24 D = -150.0 (c 1.0, CH 2Cl 2). 1 H NMR (400 MHz, CD 2Cl 2) δ 7.39 7.35 (m, 1H), 7.27 7.23 (m, 2H), 7.23 7.17 (m, 1H), 7.07 6.97 (m, 2H), 6.59 (td, J = 7.2, 0.8 Hz, 1H), 6.55 6.47 (m, 2H), 6.35 (dd, J = 16.0, 5.6 Hz, 1H), 4.41 4.31 (m, 1H), 3.50 3.34 (m, 2H), 2.94 (t, J = 8.4 Hz, 2H), 1.40 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl 3) δ 151.48, 139.47, 134.74, 132.50, 130.82, 130.22, 129.74, 127.62, 127.48, 126.47, 125.03, 124.80, 117.58, 107.91, 52.73, 47.67, 28.58, 16.50. IR (ATR): 2970, 2842, 1605, 1485, 1256, 1182, 964, 877, 740, 684cm -1. HRMS calculated for C 18H 19ClN [M+H] + 284.1201, found 284.1205. Chiral SFC: 250 mm CHIRALCEL IC, 7% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 4.1 min, t R2 (major) = 4.9 min. (R, E)-1-(4-(3-bromophenyl)but-3-en-2-yl)indoline (3ha) Colorless oil, 82% yield, 97% ee, [ ] 24 D = -120.2 (c 1.0, CH 2Cl 2). 1 H NMR (400 MHz, CD 2Cl 2) δ 7.55 7.51 (m, 1H), 7.37 7.32 (m, 1H), 7.31 7.26 (m, 1H), 7.18 (t, J = 7.6 Hz, 1H), 7.07 6.97 (m, 2H), 6.62 6.56 (m, 1H), 6.54 6.47 (m, 2H), 6.34 (dd, J = 16.0, 5.6 Hz, 1H), 4.41 4.29 (m, 1H), 3.49 3.34 (m, 2H), 2.94 (t, J = 8.4 Hz, 2H), 1.40 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl 3) δ 151.43, 139.74, 132.52, 130.84, 130.56, 130.50, 129.66, 129.43, 127.48, 125.46, 124.80, 122.99, 117.62, 107.94, 52.76, 47.67, 28.58, 16.50. IR (ATR): 2970, 2842, 1605, 1485, 1257, 1182, 964, 867, 742, cm -1. HRMS calculated for C 18H 19BrN [M+H] + 328.0696, found 328.0701. Chiral SFC: 250 mm CHIRALCEL IC, 3% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 10.1 min, t R2 (major) = 12.0 min. (R, E)-1-(4-(3-tolyl)but-3-en-2-yl)indoline (3ia) S7

Colorless oil, 80% yield, 96% ee, [ ] 24 D = -108.8 (c 1.0, CH 2Cl 2). 1 H NMR (400 MHz, CD 2Cl 2) δ 7.22 7.14 (m, 3H), 7.07 6.98 (m, 3H), 6.62 6.49 (m, 3H), 6.31 (dd, J = 16.0, 5.6 Hz, 1H), 4.42 4.30 (m, 1H), 3.50 3.36 (m, 2H), 2.94 (t, J = 8.4 Hz, 2H), 2.33 (s, 3H), 1.40 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl 3) δ 151.64, 138.60, 137.37, 131.17, 130.86, 130.43, 128.77, 128.56, 127.46, 127.28, 124.75, 123.81, 117.44, 107.96, 52.82, 47.64, 28.59, 21.47, 16.58. IR (ATR): 2922, 2850, 1605, 1486, 1255, 1052, 1023, 966, 742, 694 cm -1. HRMS calculated for C 19H 22N [M+H] + 264.1747, found 264.1745. Chiral SFC: 250 mm CHIRALCEL IC, 7% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 3.5 min, t R2 (major) = 4.1 min. (R, E)-1-(4-(2-chlorophenyl)but-3-en-2-yl)indoline (3ja) Colorless oil, 73% yield, 93% ee, [ ] 24 D = -64.0 (c 1.0, CH 2Cl 2). 1 H NMR (400 MHz, CD 2Cl 2) δ 7.51 (dd, J = 7.6, 2.0 Hz, 1H), 7.35 (dd, J = 7.6, 1.6 Hz, 1H), 7.26 7.14 (m, 2H), 7.09 6.99 (m, 2H), 6.96 (dd, J = 16.0, 1.2 Hz, 1H), 6.60 (t, J = 7.2 Hz, 1H), 6.63 6.57 (m, 1H), 6.31 (dd, J = 16.0, 6.0 Hz, 1H), 4.46 4.34 (m, 1H), 3.51 3.37 (m, 2H), 2.95 (t, J = 8.4 Hz, 2H), 1.43 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CD 2Cl 2) δ 151.47, 135.66, 133.78, 133.21, 130.85, 129.95, 128.88, 127.50, 127.45, 127.29, 127.26, 124.78, 117.62, 108.05, 52.95, 47.66, 28.60, 16.49. IR (ATR): 2970, 2842, 1605, 1485, 1259, 966, 741, 694 cm -1. HRMS calculated for C 18H 19ClN [M+H] + 284.1201, found 284.1203. Chiral SFC: 250 mm CHIRALCEL IC, 2% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 8.8 min, t R2 (major) = 9.9 min. (R, E)-1-(4-(2-tolyl)but-3-en-2-yl)indoline (3ka) Colorless oil, 69% yield, 96% ee, [ ] 24 D = -63.2 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.43 7.35 (m, 1H), 7.17 7.10 (m, 3H), 7.07 6.97 (m, 2H), 6.78 (d, J = 16.0 Hz, 1H), 6.59 (t, J = 7.5 Hz, 1H), 6.54 (d, J = 7.5 Hz, 1H), 6.15 (dd, J = 16.0, 6.0 Hz, 1H), 4.43 4.34 (m, 1H), 3.50 3.38 (m, 2H), 2.94 (t, J = 8.5 Hz, 2H), 2.31 (s, 3H), 1.42 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 151.62, 136.73, 135.79, 131.89, 130.89, 130.53, 129.19, 127.66, 127.44, 126.38, 125.91, 124.75, 117.52, 108.15, 53.16, 47.63, 28.61, 19.93, 16.76. IR (ATR): 2968, 2844, 1605, 1485, 1458, 1259, 1181, 967, 742, 711 cm -1. HRMS calculated for C 19H 22N [M+H] + 264.1747, found 264.1748. Chiral SFC: 250 mm CHIRALCEL IC, 4% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 3.8 min, t R2 (major) = 4.4 min. (R, E)-1-(4-(furan-2-yl)but-3-en-2-yl)indoline (3la) Colorless oil, 78% yield, 95% ee, [ ] 24 D = -179.4 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.33 (s, 1H), 7.07 6.96 (m, 2H), 6.59 (t, J = 7.5 Hz, 1H), 6.48 (d, J = 8.0 Hz, 1H), 6.42 6.34 (m, 2H), 6.26 6.18 (m, 2H), 4.37 4.29 (m, 1H), 3.46 3.33 (m, 2H), 2.93 (t, J = 8.5 Hz, 2H), 1.38 (t, J = 6.5 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 153.02, 151.51, 142.13, 130.82, 129.29, 127.43, 124.75, 119.60, 117.50, 111.63, 107.92, 107.81, 52.45, 47.54, 28.55, 16.51. IR (ATR): 2970, 2844, 1605, 1485, 1254, 1150, 1011, 961, 732 cm -1. HRMS calculated for C 16H 18NO [M+H] + 240.1383, found 240.1384. Chiral SFC: 250 mm CHIRALCEL IC, 2% i PrOH, 3.0 ml/min, 254 nm, 44 C, S8

nozzle pressure = 200 bar CO 2, t R1 (major) = 4.6 min, t R2 (minor) = 5.5 min. (R, E)-1-(4-(thiophen-2-yl)but-3-en-2-yl)indoline (3ma) Colorless oil, 73% yield, 92% ee, [ ] 24 D = -194.8 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.17 7.12 (m, 1H), 7.08 7.04 (m, 1H), 7.03 6.99 (m, 1H), 6.97 6.92 (m, 2H), 6.70 (dd, J = 16.0, 1.5 Hz, 1H), 6.60 (td, J = 7.5, 1.0 Hz, 1H), 6.49 (d, J = 8.0 Hz, 1H), 6.15 (dd, J = 16.0, 6.0 Hz, 1H), 4.37 4.29 (m, 1H), 3.50 3.34 (m, 2H), 2.94 (t, J = 8.5 Hz, 2H), 1.38 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 151.50, 142.63, 130.81, 130.53, 127.73, 127.47, 125.76, 124.77, 124.31, 124.29, 117.51, 107.85, 52.60, 47.64, 28.59, 16.43. IR (ATR): 2969, 2843, 1605, 1485, 1252, 1181, 955, 853, 742 cm -1. HRMS calculated for C 16H 18NS [M+H] + 256.1155, found 256.1153. Chiral SFC: 250 mm CHIRALCEL IC, 2% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (major) = 8.4 min, t R2 (minor) = 9.3 min. (R, E)-1-(undec-3-en-2-yl)indoline (3na) Colorless oil, 68% yield, 76% ee, [ ] 24 D = -46.0 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.03 6.94 (m, 2H), 6.58 6.52 (m, 1H), 6.43 (d, J = 8.0 Hz, 1H), 5.65 5.57 (m, 1H), 5.50 (dd, J = 15.5, 6.0 Hz, 1H), 4.18 4.08 (m, 1H), 3.40 3.25 (m, 2H), 2.89 (t, J = 8.5 Hz, 2H), 2.07 1.97 (m, 2H), 1.39 1.21 (m, 13H), 0.88 (t, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 151.73, 132.55, 130.81, 129.96, 127.31, 124.59, 117.10, 107.91, 52.38, 47.24, 32.79, 32.23, 29.76, 29.52, 29.43, 28.46, 23.04, 16.55, 14.26. IR (ATR): 2923, 2852, 1606, 1486, 1460, 1256, 1182, 1159, 970, 740 cm -1. HRMS calculated for C 19H 30N [M+H] + 272.2372, found 272.2370. Chiral SFC: 250 mm CHIRALCEL IC, 10% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 1.9 min, t R2 (major) = 2.1 min. (R, E)-1-(pent-3-en-2-yl)indoline (3oa) Colorless oil, 73% yield, 75% ee, [ ] 24 D = -44.8 (c 1.0, CH 2Cl 2). 1 H NMR (500 MHz, CD 2Cl 2) δ 7.06 6.94 (m, 2H), 6.56 (t, J = 7.5 Hz, 1H), 6.43 (d, J = 7.5 Hz, 1H), 5.70 5.60 (m, 1H), 5.58 5.49 (m, 1H), 4.19 4.08 (m, 1H), 3.41 3.25 (m, 2H), 2.89 (t, J = 8.5 Hz, 2H), 1.71 1.64 (m, 3H), 1.26 (d, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDCl 3) δ 151.71, 131.29, 130.85, 127.37, 126.94, 124.64, 117.18, 107.91, 52.46, 47.24, 28.50, 17.97, 16.68. IR (ATR): 2969, 2845, 1605, 1485, 1254, 1183, 1160, 964, 741, 710 cm -1. HRMS calculated for C 13H 18N [M+H] + 188.1434, found 188.1431. Chiral SFC: 250 mm CHIRALCEL IC, 0.5% i PrOH, 3.0 ml/min, 254 nm, 44 C, nozzle pressure = 200 bar CO 2, t R1 (minor) = 4.9 min, t R2 (major) = 5.2 min. 4. Synthesis of N-allylic indole 5 3 S9

To a solution of 3oa (18.7 mg, 0.10 mmol) in THF (1 ml) added DDQ (2,3-dichloro-5,6-dicyanop-benzoquinone, 25.0 mg, 0.11 mmol) and the reaction system was stirred for 10 min at room temperature. THF was removed and the pure allylic indole 5 was obtained by column chromatography (hexanes/etoac = 15:1) as a colorless oil (14.0 mg, 76% yield). [ ] 24 D = -95.2 (c 1.0, CHCl 3) [lit. 3 [ ] 24 D = -24.8 (c 1.0, CHCl 3) for R configuration, 39% ee]. 1 H NMR (400 MHz, CDCl 3) δ 7.64 (d, J = 7.6 Hz, 1H), 7.38 (d, J = 8.4 Hz, 1H), 7.23 7.17 (m, 2H), 7.13 7.06 (m, 1H), 6.55 6.48 (m, 1H), 5.74 5.66 (m, 1H), 5.63 5.52 (m, 1H), 5.09 4.99 (m, 1H), 1.69 (dt, J = 6.0, 1.2 Hz, 3H), 1.62 (d, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl 3) δ 135.62, 131.82, 128.66, 126.61, 124.56, 121.16, 120.89, 119.25, 109.79, 101.11, 52.60, 20.40, 17.61. 5. References 1) Preuß, T.; Saak, W.; Doye, S. Chem. Eur. J. 2013, 19, 3833 2) Chen, Q.-A.; Chen, Z.; Dong, V. M. J. Am. Chem. Soc. 2015, 137, 8392. 3) Zhao, Q.; Zhuo, C.-X.; You, S.-L. RSC Adv. 2014, 4, 10875 S10

6. NMR spectra (E)-2-(4-(4-methoxyphenyl)but-3-en-2-yl)-1,3-diphenylpropane-1,3-dione S11

(E)-1-methoxy-4-(3-(3-phenylpropoxy)but-1-en-1-yl)benzene S12

(E)-(4-(4-methoxyphenyl)but-3-en-2-yl)(4-tolyl)sulfane S13

(R, E)-4-chloro-1-(4-phenylbut-3-en-2-yl)indoline (3ab) S14

(R, E)-4-methyl-1-(4-phenylbut-3-en-2-yl)indoline (3ac) S15

(R, E)-4-methoxy-1-(4-phenylbut-3-en-2-yl)indoline (3ad) S16

(R, E)-5-fluoro-1-(4-phenylbut-3-en-2-yl)indoline (3ae) S17

(R, E)-5-chloro-1-(4-phenylbut-3-en-2-yl)indoline (3af) S18

(R, E)-5-bromo-1-(4-phenylbut-3-en-2-yl)indoline (3ag) S19

(R, E)-5-methoxy-1-(4-phenylbut-3-en-2-yl)indoline (3ah) S20

(R, E)-6-methyl-1-(4-phenylbut-3-en-2-yl)indoline (3ai) S21

(R, E)-6-methoxy-1-(4-phenylbut-3-en-2-yl)indoline (3aj) S22

(R, E)-1-(4-(4-fluorophenyl)but-3-en-2-yl)indoline (3ba) S23

(R, E)-1-(4-(4-chlorophenyl)but-3-en-2-yl)indoline (3ca) S24

(R, E)-1-(4-(4-bromophenyl)but-3-en-2-yl)indoline (3da) S25

(R, E)-1-(4-(4-tolyl)but-3-en-2-yl)indoline (3ea) S26

(R, E)-1-(4-(4-methoxyphenyl)but-3-en-2-yl)indoline (3fa) S27

(R, E)-1-(4-(3-chlorophenyl)but-3-en-2-yl)indoline (3ga) S28

(R, E)-1-(4-(3-bromophenyl)but-3-en-2-yl)indoline (3ha) S29

(R, E)-1-(4-(3-tolyl)but-3-en-2-yl)indoline (3ia) S30

(R, E)-1-(4-(2-chlorophenyl)but-3-en-2-yl)indoline (3ja) S31

(R, E)-1-(4-(2-tolyl)but-3-en-2-yl)indoline (3ka) S32

(R, E)-1-(4-(furan-2-yl)but-3-en-2-yl)indoline (3la) S33

(R, E)-1-(4-(thiophen-2-yl)but-3-en-2-yl)indoline (3ma) S34

(R, E)-1-(undec-3-en-2-yl)indoline (3na) S35

(R, E)-1-(pent-3-en-2-yl)indoline (3oa) S36

7. SFC spectra S37

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