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1 Supporting Information Design and Enantioselective Synthesis of β-vinyl Tryptamine Building Blocks for Construction of Privileged Chiral Indole Scaffolds Tao-Yan Lin, Hai-Hong Wu, Jian-Jun Feng*, and Junliang Zhang* Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N. Zhongshan Road, Shanghai , P. R. China. Fax:(+86) ; S1

2 Contents 1. General Information...S3 2. Experimental Procedures and Characterization Data...S4 2.1 General Procedure for [Rh(NBD)2] + BF4 - Catalyzed Intermolecular Allylic Substitution Reaction of Vinyl Aziridines (R or S)-1 and Indoles 2...S4 2.2 Synthetic Transformations of products...s Formal Synthesis of Constrained Analogue of MS S Formal Synthesis of a nnos and 5-HT1B/1D Receptor Inhibitor (-)-24cy...S39 3. References...S44 4. Crystal Structure of (R)-7aj...S H and 13 C NMR Spectra for New Compounds...S46 S2

3 1. General Information All air- and moisture-sensitive manipulations were carried out with standard Schlenk techniques under nitrogen or in a glove box under nitrogen. 1 H NMR, 13 C NMR spectra were measured at 400 MHz (or 500 MHz) and 100 MHz (or 125 MHz) in CDCl3 (or (CD3)2CO, CD3OD) using TMS signal, 0.00 ppm ((CD3)2CO: 2.05 ppm; CD3OD: 3.34 ppm), and the residual signals from CHCl3, 77.0 ppm ((CH3)2CO: ppm; CH3OH: 49.8 ppm), as internal references for 1 H and 13 C NMR respectively. Data for 1 H NMR spectra are reported as follows: chemical shift (, ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublets, dt = doublet of triplets, qd = quartet of doublets, ddd = doublet of doublet of doublets, m = multiplet), coupling constant (Hz), and integration. Tetrahydrofuran and toluene were distilled from sodium and benzophenone prior to use. Dichloromethane and 1,2-dichloroethane (DCE) was distilled from CaH2 prior to use. Chiral vinyl aziridines 1a-1j [1] and indoles (2f, [2] 2x, [2] 2k, [3] 2g, [4] 2h, [4] 2e, [5] 2n, [5] 2i, [6] 2j, [6] and 2o [6] ) were synthesized according to the reported procedure. Other starting materials were purchased from Sigma Aldrich, Alfa Aesar, Adamas-beta etc. and used without treatment. S3

4 2. Experimental Procedures and Characterization Data 2.1. General Procedure for [Rh(NBD)2] + BF4 - Catalyzed Intermolecular Allylic Substitution Reaction of Vinyl Aziridines (R or S)-1 and Indoles or pyrroles 2. To a mixture of [Rh(NBD)2] + BF4 - (4 mg, 5 mol%), vinylaziridine (R or S)-1 (0.2 mmol) and 2 (0.3 mmol) was added DCE (2.0 ml) at room temperature under nitrogen atmosphere. Upon complete consumption of (R or S)-1 (TLC monitoring, about 15 min), the solvent was removed under reduced pressure, and the residue was purified by chromatography on a short silica gel column (hexanes/etoac = 5:1, v/v) to afford the desired product 3. (R)-4-methyl-N-(3-methyl-2-(2-methyl-1H-indol-3-yl)but-3-en-1-yl)benzenesulfonamide: (R)-3aa Colorless oil. 99% yield. 1 H NMR (500 MHz, CDCl3): 8.02 (s, 1H), 7.57 (d, J = 8.0 Hz, 2H), (m, 2H), 7.20 (d, J = 8.0 Hz, 2H), 7.06 (t, J = 7.0 Hz, 1H), 6.90 (t, J = 7.5 Hz, 1H), 4.90 (s, 1H), 4.80 (s, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 2.40 (s, 3H), 2.29 (s, 3H), 1.57 (s, 3H). 13 C NMR (125 MHz, CDCl3): 144.8, 143.3, 136.5, 135.3, 133.3, 129.6, 127.0, 126.9, 121.0, 119.2, 118.5, 110.5, 110.2, 107.9, 44.4, 43.0, 22.4, 21.4, MS (EI): m/z (%) = 368 (M +, 8.66), 184 (100). HRMS calcd for C21H24N2O2S: , found: [α] 26 D = (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 6.14 min (major), min (minor). (R)-4-methyl-N-(2-(2-methyl-1H-indol-3-yl)but-3-en-1-yl)benzenesulfonamide: (R)-3ba Colorless oil. 75% yield. S4

5 1 H NMR (400 MHz, CDCl3): 8.02 (s, 1H), 7.57 (d, J = 8.4 Hz, 2H), (m, 4H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 2.40 (s, 3H), 2.28 (s, 3H). 13 C NMR (100 MHz, CDCl3): 143.3, 137.3, 136.5, 135.4, 132.8, 129.6, 126.9, 126.6, 121.0, 119.2, 118.5, 116.0, 110.6, 108.3, 45.6, 40.7, 21.4, MS (EI): m/z (%) = 354 (M +, 6.30), 229 (100). HRMS calcd for C20H22N2O2S: , found: [α] 27 D = (c 1.0, CHCl3). 99% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 6.85 min (major), min (minor). (R)-N-(2-(2-methyl-1H-indol-3-yl)but-3-en-1-yl)-4-nitrobenzenesulfonamide: (R)-3ca Yellow solid. 82% yield. 1 H NMR (500 MHz, CDCl3): 8.09 (d, J = 8.5 Hz, 2H), 7.94 (s, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.18 (d, J = 8.0 Hz, 1H), 7.16 (d, J = 8.0 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 5.12 (dt, J = 10.5 and 1.5 Hz, 1H), 5.07 (dt, J = 17.5 and 1.5 Hz, 1H), 4.57 (s, 1H), (m, 1H), 3.53 (dd, J = 12.5 and 6.0 Hz, 1H), 3.34 (dd, J = 12.0 and 10.5 Hz, 1H), 2.33 (s, 3H). 13 C NMR (125 MHz, CDCl3): 149.7, 145.1, 136.8, 135.4, 132.8, 127.8, 126.4, 123.9, 121.3, 119.3, 118.4, 116.3, 110.6, 108.0, 45.7, 40.6, HRMS (ESI) calcd for C19H19N3NaO4S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). 89% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 6.83 min (major), min (minor). S5

6 (R)-N-(2-(2-methyl-1H-indol-3-yl)but-3-en-1-yl)methanesulfonamide: (R)-3da White solid. 85% yield. 1 H NMR (500 MHz, CDCl3): 7.94 (s, 1H), 7.50 (d, J = 7.5 Hz, 1H), 7.30 (d, J = 8.0 Hz, 1H), 7.12 (t, J = 7.5 Hz, 1H), 7.05 (t, J = 7.5 Hz, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 2.80 (s, 3H), 2.41 (s, 3H). 13 C NMR (125 MHz, CDCl3): 137.2, 135.5, 132.9, 126.7, 121.3, 119.5, 118.7, 116.3, 110.7, 108.6, 45.9, 41.3, 40.1, MS (EI): m/z (%) = 278 (M +, 13.35), 170 (100). HRMS calcd for C14H18N2O2S: , found: [α] 26 D = (c 1.0, CHCl3). 77% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2- propanol = 60/40, 0.8 ml/min. Retention times: 5.94 min (major), 8.73 min (minor). (R)-4-methyl-N-(4-methyl-2-(2-methyl-1H-indol-3-yl)-3-methylenepentyl)benzenesulfonamide: (R)-3ea White solid. 75% yield. 1 H NMR (500 MHz, CDCl3): 8.01 (s, 1H), 7.58 (d, J = 8.0 Hz, 2H), 7.26 (d, J = 8.0 Hz, 1H), (m, 1H), 7.20 (d, J = 8.0 Hz, 2H), 7.05 (t, J = 7.5 Hz, 1H), 6.89 (t, J = 7.0 Hz, 1H), 5.00 (s, 1H), 4.87 (s, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 2.40 (s, 3H), 2.30 (s, 3H), (m, 1H), 0.94 (d, J = 7.0 Hz, 3H), 0.85 (d, J = 7.0 Hz, 3H). 13 C NMR (125 MHz, CDCl3): 155.2, 143.2, 136.6, 135.3, 133.1, 129.6, 127.3, 126.9, 121.0, 119.2, 118.6, 110.4, 108.2, 106.6, 44.8, 40.8, 32.2, 22.8, 21.6, 21.4, MS (EI): m/z (%) = 396 (M +, 5.72), 212 (100). HRMS calcd for C23H28N2O2S: , found: [α] 26 D = (c 1.0, CHCl3). 90% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 6.11 min (major), min (minor). S6

7 (R)-4-methyl-N-(2-(2-methyl-1H-indol-3-yl)-3-methyleneheptyl)benzenesulfonamide: (R)-3fa White solid. 82% yield. 1 H NMR (400 MHz, CDCl3): 8.02 (s, 1H), 7.57 (d, J = 8.5 Hz, 2H), (m, 2H), 7.20 (d, J = 8.0 Hz, 2H), 7.05 (t, J = 7.5 Hz, 1H), 6.89 (t, J = 7.5 Hz, 1H), 4.93 (s, 1H), 4.85 (s, 1H), (m, 1H), (m, 2H), (m, 1H), 2.40 (s, 3H), 2.29 (s, 3H), (m, 2H), (m, 2H), (m, 2H), 0.80 (t, J = 7.5 Hz, 3H). 13 C NMR (100 MHz, CDCl3): 148.9, 143.2, 136.5, 135.3, 133.1, 129.6, 127.1, 126.9, 121.0, 119.1, 118.6, 110.4, 109.0, 108.0, 44.6, 41.3, 35.2, 29.9, 22.3, 21.4, 13.9, MS (EI): m/z (%) = 410 (M +, 5.53), 84 (100). HRMS calcd for C24H30N2O2S: , found: [α] 26 D = (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 5.71 min (major), 9.81 min (minor). (R)-4-methyl-N-(2-(2-methyl-1H-indol-3-yl)-3-phenylbut-3-en-1-yl)benzenesulfonamide: (R)-3ga White solid. 98% yield. 1 H NMR (400 MHz, CDCl3): 7.88 (s, 1H), 7.55 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.0 Hz, 1H), (m, 8H), (m, 1H), (m, 1H), 5.31 (s, 1H), 5.09 (s, 1H), 4.38 (dd, J = 8.4 and 3.6 Hz, 1H), (m, 1H), (m, S7

8 1H), (m, 1H), 2.39 (s, 3H), 2.21 (s, 3H). 13 C NMR (100 MHz, CDCl3): 148.2, 143.3, 141.6, 136.5, , 129.6, 128.1, 127.4, , , 126.5, 120.9, 119.2, 118.6, 113.7, 110.5, 107.5, 44.8, 41.3, 21.4, MS (EI): m/z (%) = 430 (M +, 8.60), 246 (100). HRMS calcd for C26H26N2O2S: , found: [α] 26 D = (c 1.0, CHCl3). 99% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 6.97 min (major), min (minor). (S)-N-(2,3-dimethyl-2-(2-methyl-1H-indol-3-yl)but-3-en-1-yl)-4-methylbenzenesulfonamide: 3ha White solid. 42% yield. 1 H NMR (500 MHz, CDCl3): 7.81 (s, 1H), 7.54 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 7.5 Hz, 1H), 7.22 (d, J = 8.0 Hz, 1H), 7.19 (d, J = 8.5 Hz, 2H), 7.06 (t, J = 7.5 Hz, 1H), 6.87 (t, J = 7.0 Hz, 1H), 4.95 (s, 1H), 4.87 (s, 1H), (m, 1H), 3.51 (dd, J = 11.0 and 4.0 Hz, 1H), 3.37 (dd, J = 11.0 and 8.0 Hz, 1H), 2.45 (s, 3H), 2.39 (s, 3H), 1.63 (s, 3H), 1.50 (s, 3H). 13 C NMR (125 MHz, CDCl3): 150.4, 143.1, 136.4, 135.0, 132.2, 129.6, 127.5, 126.9, 121.1, 119.9, 119.2, 111.2, 110.2, 110.1, 50.4, 45.5, 25.1, 21.5, 20.3, MS (EI): m/z (%) = 382 (M +, 3.05), 198 (100). HRMS calcd for C22H26N2O2S: , found: [α] 26 D = (c 1.0, CHCl3). 88% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2- propanol = 90/10, 0.8 ml/min. Retention times: min (major), min (minor). (S)- S8

9 (R,E)-N-(5-((tert-butyldimethylsilyl)oxy)-2-(2-methyl-1H-indol-3-yl)pent-3-en-1-yl)-4- methylbenzenesulfonamide: (R)-3ia Colorless oil. 72% yield. 1 H NMR (400 MHz, CDCl3): 7.96 (s, 1H), 7.58 (d, J = 8.4 Hz, 2H), (m, 4H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 4.27 (dd, J = 8.0 and 3.6 Hz, 1H), 4.09 (d, J = 4.8 Hz, 2H), (m, 1H), (m, 1H), (m, 1H), 2.41 (s, 3H), 2.29 (s, 3H), 0.87 (s, 9H), 0.02 (s, 3H), 0.01(s, 3H). 13 C NMR (100 MHz, CDCl3): 143.2, 136.6, 135.4, 132.7, 131.0, 129.6, 129.1, 127.0, 126.6, 121.1, 119.3, 118.7, 110.5, 108.7, 63.4, 46.0, 39.5, 25.9, 21.5, 18.3, 12.0, MS (EI): m/z (%) = 430 (M +, 8.60), 246 (100). HRMS calcd for C28H28N2NaO2S: , found: [α] 25 D = (c 1.0, CHCl3). 96% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2- propanol = 60/40, 0.8 ml/min. Retention times: 4.53 min (major), 6.75 min (minor). (R,E)-N-(2-(1-allyl-1H-indol-3-yl)-4-phenylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)-3jb Colorless oil. 90% yield. 1 H NMR (500 MHz, CDCl3): 7.67 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.0 Hz, 1H), (m, 9H), (m, 1H), 6.88 (s, 1H), 6.45 (d, J = 16.0 Hz, 1H), 6.28 (dd, J = 16.0 and 7.5 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 4.66 (dt, J = 5.5 and 1.5 Hz, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 2.41 (s, 3H). 13 C NMR (125 MHz, CDCl3): 143.4, 136.8, 136.8, 136.7, 133.2, 131.7, 129.7, 129.3, 128.5, 127.5, 127.1, 126.7, 126.3, 125.4, 122.0, , , 117.6, 113.3, 109.9, 48.8, 46.7, 40.5, MS (EI): m/z (%) = 430 (M +, 8.60), 246 (100). HRMS calcd for C28H28N2NaO2S: , found: [α] 25 D = +3.1 (c 0.5, CHCl3). 92% ee. HPLC analysis of the product: Daicel Chiralpak ADH column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 9.78 min (major), min (minor) S9

10 (R)-N-(2-(1-allyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)-3ab White solid. 89% yield. 1 H NMR (400 MHz, CDCl3): 7.69 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.0 Hz, 1H), (m, 3H), (m, 1H), (m, 1H), 6.81 (s, 1H), (m, 1H), (m, 1H), (m, 1H), 4.93 (s, 1H), 4.87 (s, 1H), (m, 2H), 3.63 (t, J =7.6 Hz, 1H), (m, 2H), 2.41 (s, 3H), 1.55 (s, 3H). 13 C NMR (100 MHz, CDCl3): 144.5, 143.3, 136.8, 136.5, 133.3, 129.6, 127.2, 127.0, 125.4, 121.8, 119.2, 119.1, 117.2, 112.9, 112.3, 109.7, 48.6, 44.6, 43.7, 21.4, MS (EI): m/z (%) = 394 (M +, 9.05), 243 (100). HRMS calcd for C23H26N2O2S: , found: [α] 27 D = (c 1.0, CHCl3). 96% ee. HPLC analysis of the product: Daicel Chiralpak ADH column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 7.58 min (minor), 8.12 min (major). (R)-tert-butyl -2-methyl-3-(3-methyl-1-((4-methylphenyl)sulfonamido)but-3-en-2-yl)-1H-indole-1- carboxylate: (R)-3ac Colorless oil. 63% yield. 1 H NMR (500 MHz, CDCl3): 8.10 (d, J = 8.0 Hz, 1H), 7.57 (d, J = 7.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 1H), (m, 3H), (m, 1H), 4.98 (s, 1H), 4.85 (s, 1H), (m, 1H), (m, 2H), (m, 1H), 2.50 (s, 3H), 2.40 (s, S10

11 3H), 1.70 (s, 9H), 1.57 (s, 3H). 13 C NMR (125 MHz, CDCl3): 150.4, 143.9, 143.3, 136.6, 135.9, 135.7, 129.6, 128.0, 126.9, 123.4, 122.2, 118.6, 115.4, 114.4, 110.8, 84.0, 44.0, 42.7, 28.2, 22.6, 21.5, MS (EI): m/z (%) = 468 (M +, 2.14), 184 (100). HRMS calcd for C26H32N2O4S: , found: [α] 26 D = (c 1.0, CHCl3). 95% ee. HPLC analysis of the product: Daicel Chiralpak ASH column; hexane/2-propanol = 80/20, 0.8 ml/min. Retention times: min (minor), min (major). (R)-4-methyl-N-(3-methyl-2-(1-methyl-1H-indol-3-yl)but-3-en-1-yl)benzenesulfonamide: (R)-3ad White solid. 85% yield. 1 H NMR (500 MHz, CDCl3): 7.67 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.0 Hz, 1H), (m, 3H), (m, 1H), (m, 1H), 6.76 (s, 1H), 4.92 (s, 1H), 4.86 (s, 1H), 4.59 (t, J = 6.0 Hz, 1H), 3.69 (s, 3H), 3.61 (t, J = 7.5 Hz, 1H), 3.38 (d, J = 6.0 Hz, 1H), 3.36 (d, J = 6.0 Hz, 1H), 2.40 (s, 3H), 1.56 (s, 3H). 13 C NMR (125 MHz, CDCl3): 144.6, 143.3, 137.1, 136.7, 129.6, 127.0, 126.9, 126.5, 121.7, 119.1, 118.9, 112.3, 112.1, 109.3, 44.7, 43.6, 32.6, 21.4, MS (EI): m/z (%) = 368 (M +, 10.42), 184 (100). HRMS calcd for C21H24N2O2S: , found: [α] 26 D = (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 7.77 min (minor), 8.31 min (major). S11

12 (R)-4-methyl-N-(3-methyl-2-(2-vinyl-1H-indol-3-yl)but-3-en-1-yl)benzenesulfonamide: (R)-3ae White solid. 79% yield. 1 H NMR (400 MHz, CDCl3): 8.39 (s, 1H), 7.58 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.4 Hz, 1H), 7.20 (d, J = 8.0 Hz, 2H), (m, 1H), (m, 1H), 6.69 (dd, J = 17.6 and 11.2 Hz, 1H), 5.52 (d, J = 17.6 Hz, 1H), 5.24 (d, J = 11.2 Hz, 1H), 4.94 (s, 1H), 4.85 (s, 1H), (m, 1H), (m, 2H), (m, 1H), 2.40 (s, 3H), 1.57 (s, 3H). 13 C NMR (100 MHz, CDCl3): 144.5, 143.3, 136.5, 136.3, 134.1, 129.6, 127.0, 126.9, 124.9, 123.0, 119.7, 119.6, 113.0, 111.6, 110.9, 110.5, 44.6, 42.7, 22.5, MS (EI): m/z (%) = 380 (M +, 11.71), 196 (100). HRMS calcd for C22H24N2O2S: , found: [α] 26 D = (c 1.0, CHCl3). 97% ee. HPLC analysis of the product: Daicel Chiralpak ADH column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 6.79 min (major), min (minor). (R)-N-(2-(2-allyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)-3af Colorless oil. 86% yield. 1 H NMR (400 MHz, CDCl3): 8.07 (s, 1H), 7.58 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.4 Hz, 1H), 7.25 (d, J = 8.4 Hz, 1H), 7.20 (d, J = 8.4 Hz, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 4.93 (s, 1H), 4.83 (s, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), 2.39 (s, 3H), 1.58 (s, 3H). 13 C NMR (100 MHz, CDCl3): 144.7, 143.2, 136.5, 135.5, 134.7, 134.6, 129.6, , , 121.3, 119.3, 119.0, 117.5, 110.7, 110.3, 108.1, 44.5, 42.9, 30.5, 22.6, MS (EI): m/z (%) = 394 (M +, 12.30), 210 (100). HRMS calcd for C23H26N2O2S: , found: [α] 27 D = (c 1.0, CHCl3). 97% ee. HPLC analysis of the product: Daicel Chiralpak OD-3 column; hexane/2-propanol = 80/20, 0.8 ml/min. Retention times: 8.97 min (major), min (minor). S12

13 (R,E)-4-methyl-N-(3-methyl-2-(2-(3-oxobut-1-en-1-yl)-1H-indol-3-yl)but-3-en-1-yl)benzenesulfonamide: (R)-3ag Yellow solid. 79% yield. 1 H NMR (400 MHz, CDCl3): 9.40 (s, 1H), 7.72 (d, J = 16.4 Hz, 1H), 7.64 (d, J = 8.0 Hz, 2H), 7.47 (d, J = 8.0 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 7.23 (d, J = 8.0 Hz, 2H), (m, 1H), 6.97 (t, J = 7.6 Hz, 1H), 6.60 (d, J = 16.0 Hz, 1H), 5.03 (s, 1H), 4.97 (s, 1H), (broad s, 1H), (m, 1H), (m, 1H), (m, 1H), 2.40 (s, 3H), 2.33 (s, 3H), 1.61 (s, 3H). 13 C NMR (100 MHz, CDCl3): 199.1, 144.5, 143.4, 137.9, 136.7, 131.7, 131.5, 129.7, 127.1, 126.9, , , 120.2, 120.1, 119.3, 111.7, 111.0, 45.0, 43.3, 26.3, 22.8, MS (EI): m/z (%) = 422 (M +, 4.89), 91 (100). HRMS calcd for C24H26N2O3S: , found: [α] 26 D = (c 1.0, CHCl3). 97% ee. HPLC analysis of the product: Daicel Chiralpak ADH column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 6.03 min (major), 7.96 min (minor). (R,E)-ethyl -3-(3-(3-methyl-1-((4-methylphenyl)sulfonamido)but-3-en-2-yl)-1H-indol-2-yl)acrylate: (R)-3ah Yellow solid. 77% yield. S13

14 1 H NMR (500 MHz, CDCl3): (m, 1H), 7.75 (d, J = 16.0 Hz, 1H), 7.59 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5 Hz, 1H), 7.32 (d, J = 8.0 Hz, 1H), (m, 3H), 6.95 (t, J = 7.5 Hz, 1H), 6.27 (d, J = 15.5 Hz, 1H), 4.98 (s, 1H), 4.90 (s, 1H), (m, 1H), 4.23 (q, J = 7.0 Hz, 2H), (m, 1H), (m, 1H), (m, 1H), 2.39 (s, 3H), 1.57 (s, 3H), 1.32 (t, J = 7.5 Hz, 1H). 13 C NMR (125 MHz, CDCl3): 166.9, 144.1, 143.3, 137.5, 136.4, 131.5, 131.4, 129.6, , , 124.8, 120.4, 120.1, 118.2, 116.0, 111.5, 111.1, 60.7, 44.9, 42.9, 22.6, 21.4, HRMS (ESI) calcd for C25H28N2NaO4S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). 97% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 7.27 min (major), 8.07 min (minor). (R,E)-N-(2-(2-(3-hydroxyprop-1-en-1-yl)-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzene sulfonamide: (R)-3ai Yellow oil. 90% yield. 1 H NMR (400 MHz, CDCl3): 8.71 (s, 1H), 7.55 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.0 Hz, 1H), (m, 1H), 7.15 (d, J = 8.0 Hz, 2H), 7.10 (t, J = 7.6 Hz, 1H), 6.89 (t, J = 7.2 Hz, 1H), 6.71 (d, J = 15.6 Hz, 1H), 6.18 (dt, J = 16.0 and 5.6 Hz, 1H), 4.93 (s, 1H), 4.84 (s, 1H), (m, 1H), 4.27 (d, J = 5.2 Hz, 1H), (m, 2H), (m, 1H), 2.88 (s, 1H), 2.36 (s, 3H), 1.55 (s, 3H). 13 C NMR (100 MHz, CDCl3): 144.7, 143.3, 136.6, 136.4, 133.7, 129.6, 128.3, 127.0, 126.9, 122.8, 119.6, , , 111.5, 111.0, 110.5, 63.3, 44.7, 42.8, 22.7, MS (EI): m/z (%) = 410 (M +, 8.64), 44 (100). HRMS calcd for C23H26N2O3S: , found: [α] 26 D = (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 7.63 min (major), min (minor). S14

15 (R)-N-(2-(2-(hydroxymethyl)-1-methyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzene sulfonamide: (R)-3aj Colorless oil. 84% yield. 1 H NMR (400 MHz, CDCl3): 7.48 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.0 Hz, 1H), (m, 1H), (m, 1H), 7.07 (d, J = 8.0 Hz, 2H), (m, 1H), 4.99 (broad s, 1H), 4.96 (s, 1H), 4.89 (s, 1H), (m, 2H), 3.75 (s, 3H), (m, 2H), 3.37 (t, J = 12.4 Hz, 1H), 2.99 (s, 1H), 2.33 (s, 3H), 1.58 (s, 3H). 13 C NMR (100 MHz, CDCl3): 145.1, 143.1, 137.4, 137.1, 136.5, 129.4, 126.7, 125.4, 122.0, 119.8, 119.0, 110.2, 110.0, 109.3, 53.5, 44.8, 43.3, 29.7, 22.8, HRMS (ESI) calcd for C22H26N2NaO3S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 6.77 min (major), 9.35 min (minor). (R)-N-(2-(2-((allyloxy)methyl)-1-methyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)-3ak Colorless oil. 89% yield. 1 H NMR (400 MHz, CDCl3): 7.43 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.0 Hz, 1H), 7.25 (d, J = 8.0 Hz, 1H), (m, 1H), 7.03 (d, J = 8.0 Hz, 2H), (m, 1H), (m, 1H), 5.34 (dd, J = 16.8 and 1.2 Hz, 1H), 5.26 (dd, J = 10.4 and 1.2 Hz, 1H), 4.97 (s, 1H), 4.90 (s, 1H), (m, 1H), 4.57 (s, 2H), S15

16 (m, 2H), 3.73 (s, 3H), (m, 2H), (m, 1H), 2.32 (s, 3H), 1.58 (s, 3H). 13 C NMR (100 MHz, CDCl3): 144.6, 142.7, 137.3, 136.4, 134.2, 134.1, 129.2, 126.7, 125.3, 122.0, 119.7, 119.0, 118.1, 111.1, 110.5, 109.2, 71.5, 60.5, 44.7, 42.8, 29.7, 22.8, MS (EI): m/z (%) = 438 (M +, 2.95), 243 (100). HRMS calcd for C25H30N2O3S: , found: [α] 27 D = (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak ADH column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 6.35 min (major), 6.86 min (minor). Ethyl-(R)-5-methoxy-1-methyl-3-(3-methyl-1-((4-methylphenyl)sulfonamido)but-3-en-2-yl)-1Hindole-2-carboxylate: (R)-3al Colorless oil. 73% yield. 1 H NMR (500 MHz, CDCl3): 7.40 (d, J = 8.4 Hz, 2H), 7.18 (d, J = 9.2 Hz, 1H), 6.99 (d, J = 8.0 Hz, 2H), (m, 1H), (m, 1H), 4.99 (s, 1H), 4.90 (s, 1H), (m, 1H), 4.43 (q, J = 7.2 Hz, 2H), (m, 1H), 3.90 (s, 3H), (m, 1H), 3.67 (s, 3H), (m, 1H), 2.32 (s, 3H), 1.54 (s, 3H), 1.43 (t, J = 7.2 Hz, 3H). 13 C NMR (125 MHz, CDCl3): 162.5, 153.8, 144.7, 142.7, 136.3, 134.2, 129.1, 127.5, 126.6, 124.9, 118.8, 116.3, 111.1, 110.1, 101.1, 61.2, 55.4, 44.8, 42.1, 32.3, 22.9, 21.3, HRMS (ESI) calcd for C25H30N2NaO5S [(M+Na + )]: , found: [α] 25 D = (c 1.0, CHCl3). 95% ee. HPLC analysis of the product: Daicel Chiralpak IA column; hexane/2- propanol = 90/10, 0.8 ml/min. Retention times: min (major), min (minor). S16

17 (R)-N-(2-(4-bromo-1-methyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)-3am Colorless oil. 99% yield. 1 H NMR (500 MHz, CDCl3): 7.65 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 1.5 Hz, 1H), 7.25 (d, J = 8.5 Hz, 2H), (m, 1H), 7.10 (d, J = 9.0 Hz, 1H), 6.80 (s, 1H), 4.92 (s, 1H), 4.84 (s, 1H), (m, 1H), 3.67 (s, 3H), 3.49 (t, J =7.5 Hz, 1H), (m, 2H), 2.42 (s, 3H), 1.54 (s, 3H). 13 C NMR (125 MHz, CDCl3): 144.2, 143.4, 136.6, 135.8, 129.7, 128.5, 127.8, 126.9, 124.5, 121.5, 112.5, 112.3, 111.9, 110.8, 44.6, 43.4, 32.8, 21.5, MS (EI): m/z (%) = 446 (M +, 4.08), 84 (100). HRMS calcd for C21H23N2O2S 79 Br: , found: [α] 26 D = (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 7.87 min (minor), 9.37 min (major). (R)-4-methyl-N-(3-methyl-2-(1-methyl-4-vinyl-1H-indol-3-yl)but-3-en-1-yl)benzenesulfonamide: (R)-3an White solid. 80% yield. 1 H NMR (400 MHz, CDCl3): 7.68 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), (m, 4H), 6.77 (s, 1H), 5.57 (dd, J = 17.2 and 1.6 Hz, 1H), 5.21 (dd, J = 11.2 and 2.0 Hz, 1H), 4.96 (s, 1H), 4.71 (s, 1H), 4.64 (t, J = 5.6 Hz, 1H), 3.86 (t, J = 7.2 Hz, 1H), 3.68 (s, 3H), 3.32 (t, J = 6.0 Hz, 2H), 2.41 (s, 3H), 1.64 (s, 3H). 13 C NMR (100 MHz, CDCl3): 145.2, 143.3, 137.6, 136.7, 135.9, 132.3, 129.6, 127.3, 127.0, 124.6, 121.9, 117.6, 115.7, 113.4, 113.1, 108.8, 45.5, 44.0, 32.8, MS (EI): m/z (%) = 394 (M +, 7.38), 210 (100). HRMS calcd for C23H26N2O2S: , found: [α] 27 D = (c 1.0, CHCl3). 97% ee. HPLC analysis of the product: Daicel Chiralpak OZ-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: min (minor), min (major). S17

18 (R)-N-(2-(4-(hydroxymethyl)-1-methyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)-3ao Colorless oil. 50% yield. 1 H NMR (400 MHz, CDCl3): 7.61 (d, J = 8.0 Hz, 2H), (m, 1H), 7.20 (d, J = 8.4 Hz, 2H), (m, 1H), 7.00 (d, J = 7.2 Hz, 1H), 6.79 (s, 1H), (m, 1H), (m, 1H), 4.89 (s, 1H), 4.74 (s, 1H), (m, 1H), 4.01 (t, J = 7.2 Hz, 1H), 3.67 (s, 3H), (m, 2H), 2.39 (s, 3H), 2.34 (s, 1H), 1.64 (s, 3H). 13 C NMR (100 MHz, CDCl3): 146.3, 143.0, 137.6, 136.8, 132.6, 129.5, 127.3, 127.0, 125.3, 121.4, 120.4, 113.7, 111.6, 109.6, 64.0, 46.6, 43.2, 32.8, 21.7, HRMS (ESI) calcd for C22H26N2NaO3S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). 95% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 80/20, 0.8 ml/min. Retention times: 9.41 min (minor), min (major). (R)-N-(2-(5-fluoro-1-methyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)-3ap White solid. 95% yield. 1 H NMR (500 MHz, CDCl3): 7.66 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 7.14 (dd, J = 9.0 and 4.5 Hz, 1H), 6.97 (dd, J = 9.5 and 2.0 Hz, 1H), 6.92 (ddd, J S18

19 = 9.5, 9.0 and 2.5 Hz, 1H), 6.83 (s, 1H), 4.92 (s, 1H), 4.85 (s, 1H), 4.61 (t, J = 6.0 Hz, 1H), 3.69 (s, 3H), 3.51 (t, J = 7.5 Hz, 1H), (m, 2H), 2.41 (s, 3H), 1.54 (s, 3H). 13 C NMR (125 MHz, CDCl3): (d, J = Hz), 144.3, 143.4, 136.6, 133.8, 129.6, 128.2, 127.1, 127.0, 112.3, (d, J = 4.6 Hz), 110.2, (d, J = 9.9 Hz), (d, J = 23.5 Hz), 44.5, 43.6, 32.9, 21.4, F NMR (470.5 MHz, CDCl3): HRMS (ESI) calcd for C21H23FN2NaO2S [(M+Na + )]: , found: [α] 27 D = (c 1.0, CHCl3). 96% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 7.68 min (minor), 8.64 min (major). (R)-N-(2-(5-methoxy-1-methyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)-3aq White solid. 90% yield. 1 H NMR (400 MHz, CDCl3): 7.66 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), (m, 1H), (m, 2H), 6.74 (s, 1H), 4.93 (s, 1H), 4.86 (s, 1H), 4.60 (t, J = 6.0 Hz, 1H), 3.78 (s, 3H), 3.66 (s, 3H), 3.58 (t, J = 7.6 Hz, 1H), (m, 2H), 2.40 (s, 3H), 1.57 (s, 3H). 13 C NMR (100 MHz, CDCl3): 153.6, 144.6, 143.3, 136.7, 132.5, 129.6, 127.2, 127.1, 127.0, 111.9, 111.8, 111.7, 111.0, 101.0, 55.7, 44.6, 43.6, 32.8, 21.4, MS (EI): m/z (%) = 398 (M +, 15.81), 214 (100). HRMS calcd S19

20 for C22H26N2O3S: , found: [α] 28 D = -7.3 (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: min (minor), min (major). (R)-N-(2-(6-chloro-1-methyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)-3ar White solid. 87% yield. 1 H NMR (500 MHz, CDCl3): 7.65 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 1H), (m, 3H), 6.96 (dd, J = 8.5 and 1.5 Hz, 1H), 6.78 (s, 1H), 4.92 (s, 1H), 4.85 (s, 1H), 4.64 (t, J = 6.0 Hz, 1H), 3.65 (s, 3H), 3.57 (t, J = 7.0 Hz, 1H), (m, 2H), 2.41 (s, 3H), 1.54 (s, 3H). 13 C NMR (125 MHz, CDCl3): 144.4, 143.4, 137.5, 136.6, 129.6, 127.8, 127.2, 127.0, 125.5, 120.0, 119.6, 112.7, 112.4, 109.3, 44.6, 43.6, 32.7, 21.4, HRMS (ESI) calcd for C21H23ClN2NaO2S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 70/30, 0.8 ml/min. Retention times: min (minor), min (major). (R)-N-(2-(1,7-dimethyl-1H-indol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: 3as Colorless oil. 94% yield. 1 H NMR (400 MHz, CDCl3): 7.68 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), (m, 1H), (m, 2H), 6.64 (s, 1H), 4.92 (s, 1H), 4.84 (s, 1H), 4.56 (t, J = 6.0 Hz, 1H), 3.96 (s, 3H), 3.57 (t, J = 7.2 Hz, 1H), (m, 2H), 2.71 (s, 3H), 2.41 (s, 3H), 1.55 (s, 3H). 13 C NMR (100 MHz, CDCl3): 144.6, 143.3, 136.8, 135.8, 129.6, 128.1, 127.1, 124.4, 121.3, 119.2, 117.1, 112.1, 112.0, 44.7, 43.5, 36.6, 21.5, 20.8, MS (EI): m/z (%) = 382 (M +, 8.82), 57 (100). HRMS calcd for C22H26N2O2S: , found: [α] 27 D = (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD- 3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 7.03 min (minor), 7.79 min (major). (R)- S20

21 (R)-methyl-1-methyl-3-(1-(4-nitrophenylsulfonamido)but-3-en-2-yl)-1H-indole-4-carboxylate: (R)- 3ct Yellow solid. 93% yield. 1 H NMR (500 MHz, CDCl3): 7.97 (d, J = 9.0 Hz, 2H), 7.65 (d, J = 9.0 Hz, 2H), (m, 1H), 7.34 (dd, J = 8.5 and 1.0 Hz, 1H), 7.18 (t, J = 8.0 Hz, 1H), 6.87 (s, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 1H), 3.93 (s, 3H), 3.67 (s, 3H), (m, 2H). 13 C NMR (125 MHz, CDCl3): 169.6, 149.2, 146.0, 138.8, 137.7, 129.7, 127.5, 124.5, 123.4, 123.3, 123.2, 120.7, 115.2, 114.5, 113.8, 52.5, 48.7, 38.9, HRMS (ESI) calcd for C21H21N3NaO6S [(M+Na + )]: , found: [α] 25 D = (c 0.5, CHCl3). 96% ee. HPLC analysis of the product: Daicel Chiralpak IB column; hexane/2- propanol = 80/20, 0.8 ml/min. Retention times: min (major), min (minor). (R)-ethyl-5-methoxy-1-methyl-3-(1-(4-nitrophenylsulfonamido)but-3-en-2-yl)-1H-indole-2- carboxylate: (R)-3cl Yellow solid. 60% yield. 1 H NMR (500 MHz, CDCl3): 7.83 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 8.5 Hz, 2H), 7.05 (d, J = 9.0 Hz, 1H), 6.90 (dd, J = 9.0 and 2.5 Hz, 1H), 6.72 (d, J = 2.5 Hz, 1H), (m, 1H), 5.57 (s, 1H), 5.17 (d, J = 9.5 Hz, 1H), 5.10 (d, S21

22 J = 17.5 Hz, 1H), (m, 3H), 3.84 (s, 3H), 3.75 (s, 3H), (m, 1H), (m, 1H), 1.46 (d, J = 7.5 Hz, 3H). 13 C NMR (125 MHz, CDCl3): 162.6, 153.9, 149.1, 145.0, 136.7, 133.9, 127.3, 126.8, 124.4, 123.1, 119.4, 116.3, 115.9, 111.2, 102.5, 61.6, 55.6, 46.1, 39.2, 32.3, HRMS (ESI) calcd for C23H25N3NaO7S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). Note: The ee value of (R)-3cl can not be determined by HPLC analysis using a chiral stationary phase. The ee value of (R)-3cl was determined by chiral-phase HPLC analysis after conversion it into (R)-15cl. (R)-N-(2-(2,5-dimethyl-1H-pyrrol-3-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)- 3au Colorless oil. 62% yield. 1 H NMR (400 MHz, CDCl3): 7.71 (d, J = 8.4 Hz, 2H), 7.57 (s, 1H), 7.30 (d, J = 8.0 Hz, 2H), (m, 1H), 4.75 (s, 1H), 4.66 (s, 1H), 4.42 (s, 1H), (m, 1H), (m, 1H), 3.05 (t, J = 9.2 Hz, 1H), 2.43 (s, 3H), 2.14 (s, 3H), 2.03 (s, 3H), 1.56 (s, 3H). 13 C NMR (100 MHz, CDCl3): 145.9, 143.2, 136.9, 129.6, 127.2, 125.6, 123.3, 116.5, 110.5, 104.1, 45.4, 43.4, 21.5, 20.9, 12.9, HRMS (ESI) calcd for C18H24N2NaO2S [(M+Na + )]: , found: [α] 25 D = +1.7 (c 1.0, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak ID column; hexane/2-propanol = 90/10, 0.8 ml/min. Retention times: min (major), min (minor). (S)-N-(2-(3,4-diethyl-1H-pyrrol-2-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: 3av Colorless oil. 68% yield. Note: the reaction of (R)-1a with 2v was carried out as following: To a mixture of [Rh(NBD)2] + BF4 - (4 mg, 5 mol%), 2v (148 mg, 1.2 mmol) was added DCE (1.0 ml), then a solution of (R)-1a (48 mg, 0.2 mmol) in DCE (1.5 ml) was added dropwisely over 10 min at room temperature under nitrogen atmosphere. Upon complete consumption of (R)-1a (TLC monitoring, about 15 min), the solvent was removed under reduced pressure, and the residue was purified by chromatography on a short silica gel column (hexanes/etoac = 5:1, v/v) to afford the desired product (S)-3av (49 mg, 68%) together with (S,S)-22av (10 mg, 17%). ((S)-3av : (S,S)-22av = 8:1) (S)- S22

23 1 H NMR (400 MHz, CDCl3): 7.69 (d, J = 7.6 Hz, 2H), 7.55 (s, 1H), 7.30 (d, J = 8.0 Hz, 2H), (m, 1H), 4.94 (s, 1H), 4.74 (s, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 2.42 (s, 3H), 2.41 (q, J = 7.6 Hz, 2H), 2.33 (q, J = 7.6 Hz, 2H), 1.59 (s, 3H), 1.78 (t, J = 7.6 Hz, 3H), 1.02 (t, J = 7.6 Hz, 3H). 13 C NMR (100 MHz, CDCl3): 144.6, 143.5, 136.7, 129.7, 127.1, 125.2, 123.9, 121.9, 113.2, 111.0, 45.0, 42.9, 22.6, 21.5, 18.4, 17.1, 16.0, HRMS (ESI) calcd for C20H28N2NaO2S [(M+Na + )]: , found: [α] 25 D = +3.6 (c 0.5, CHCl3). 97% ee. HPLC analysis of the product: Daicel Chiralpak IA column; hexane/2-propanol = 90/10, 0.8 ml/min. Retention times: min (major), min (minor). N,N'-((2S,2'S)-(3,4-diethyl-1H-pyrrole-2,5-diyl)bis(3-methylbut-3-ene-2,1-diyl))bis(4- methylbenzenesulfonamide): (S,S)-22av 1 H NMR (400 MHz, CDCl3): 7.70 (d, J = 8.0 Hz, 4H), 7.35 (s, 1H), 7.30 (d, J = 8.0 Hz, 4H), 4.89 (s, 2H), 4.66 (s, 2H), 4.46 (t, J = 6.0 Hz, 2H), 3.36 (t, J = 7.6 Hz, 2H), (m, 2H), (m, 2H), 2.42 (s, 6H), 2.27 (q, J = 7.6 Hz, 4H), 1.53 (s, 6H), 1.00 (t, J = 7.6 Hz, 6H). 13 C NMR (100 MHz, CDCl3): 144.3, 143.5, 136.8, 129.7, 127.1, 123.0, 122.5, 111.4, 44.8, 43.0, 22.3, 21.5, 17.2, HRMS (ESI) calcd for C32H43N3NaO4S2 [(M+Na + )]: , found: [α] 23 D = (c 1.0, CHCl3). (S)-N-(2-(3,5-dimethyl-1H-pyrrol-2-yl)-3-methylbut-3-en-1-yl)-4-methylbenzenesulfonamide: (R)- 3aw Colorless oil. 98% yield. 1 H NMR (500 MHz, CDCl3): 7.69 (d, J = 8.0 Hz, 2H), 7.38 (s, 1H), 7.30 (d, J = 8.0 Hz, 1H), (m, 1H), 4.92 (s, 1H), 4.72 (s, 1H), 4.47 (t, J = 6.0 Hz, 1H), 3.37 (t, J = 7.5 Hz, 1H), (m, 1H), (m, 1H), 2.43 (s, 3H), 2.13 (s, 3H), 1.91 (s, 3H), 1.60 (s, 3H). 13 C NMR (125 MHz, CDCl3): 144.5, 143.5, 136.6, 129.7, 127.1, 126.3, 122.5, 116.5, 110.8, 108.3, 44.8, 42.8, 22.4, 21.5, 12.9, HRMS (ESI) calcd for C18H24N2NaO2S [(M+Na + )]: , found: [α] 25 D = +9.8 (c 1.0, CHCl3). 97% ee. HPLC analysis of the product: Daicel Chiralpak IB column; hexane/2-propanol = 90/10, 0.8 ml/min. Retention times: 9.51 min (major), min (minor). S23

24 2.2. Synthetic Transformations of products. Procedure: To a solution of (R)-3aa (74 mg, 0.2 mmol) in MeOH (4 ml) was added 10% Pd/C (7.4 mg) at room temperature. The reaction flask was evacuated twice under reduced pressure, and a H2 balloon was placed on the top. After stirring at room temperature for 5 h, the mixture was filtered through celite and the filtrate was concentrated and the residue was purified by column chromatography on a silica gel column (hexanes/etoac = 5/1) to afford the desired product (R)-4aa (68 mg, 92%). (R)-4-methyl-N-(3-methyl-2-(2-methyl-1H-indol-3-yl)butyl)benzenesulfonamide: (R)-4aa White solid. 92% yield. 1 H NMR (400 MHz, CDCl3): 7.96 (s, 1H), 7.49 (d, J = 8.0 Hz, 2H), (m, 1H), 7.18 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 8.0 Hz, 1H), 7.07 (t, J = 7.6 Hz, 1H), 6,85 (t, J = 7.6 Hz, 1H), 4.04 (d, J = 9.6 Hz, 1H), (m, 1H), 3.17 (t, J = 11.6 Hz, 1H), (m, 1H), 2.41 (s, 3H), 2.29 (s, 3H), (m, 1H), 1.02 (d, J = 6.4 Hz, 3H), 0.66 (d, J = 6.8 Hz, 3H). 13 C NMR (100 MHz, CDCl3): 143.1, 136.3, 135.6, 133.6, 129.5, 127.0, 126.5, 121.0, 119.1, 118.7, 110.6, 109.3, 44.7, 44.5, 30.8, 21.6, 21.5, 21.2, HRMS (ESI) calcd for C21H26N2NaO2S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). 97% S24

25 ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 5.59 min (major), 9.93 min (minor). Procedure: A solution of (R)-3ca (39 mg, 0.1 mmol) and ethyl acrylatein (20 mg, 0.2 mmol) in CH2Cl2 (0.5 ml) was added via syringe to a stirring solution of Grubbs second-generation catalyst (0.01 mmol, 8.4 mg) in CH2Cl2 (0.3 ml). The flask was fitted with a condenser and refluxed under nitrogen for 9 h. The reaction mixture was purified on silica gel column, eluting with hexane:etoac (3:1) to afford the desired product (R)-3ka (39 mg, 85%). (R,E)-ethyl -4-(2-methyl-1H-indol-3-yl)-5-((4-nitrophenyl)sulfonamido)pent-2-enoate: (R)-3ka White solid. 85% yield. 1 H NMR (400 MHz, CDCl3): 8.15 (d, J = 8.8 Hz, 2H), 8.03 (s, 1H), 7.76 (d, J = 8.8 Hz, 2H), 7.23 (d, J = 8.4 Hz, 1H), (m, 3H), 6.90 (t, J = 7.6 Hz, 1H), 5.78 (dd, J = 15.6 and 1.6 Hz, 1H), (m, 1H), 4.14 (q, J = 7.2 Hz, 2H), (m, 1H), (m, 1H), (m, 1H), 2.35 (s, 3H), 1.23 (t, J = 7.2 Hz, 3H). 13 C NMR (100 MHz, CDCl3): 166.2, 149.9, 146.1, 145.2, 135.4, 133.4, 127.9, 126.1, 124.1, 122.7, 121.7, 119.8, 118.2, 110.8, 106.6, 60.5, 45.3, 39.7, 14.1, HRMS (ESI) calcd for C22H23N3NaO6S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). 86% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 8.18 min (major), min (minor). S25

26 Procedure: To a stirred solution of indole 3ae (59 mg, mmol) in dry DMF (2.0 ml), NaH (19 mg, 60% suspension in mineral oil, mmol) was added under nitrogen atmosphere at 0 o C. The reaction mixture was then warmed to room temperature and stirred for 30 min. After cooling to 0 o C, MeI (66 mg, mmol) was added dropwise to the reaction mixture. The reaction mixture was warmed to room temperature and stirred overnight. Water was added and the aqueous layer was extracted with ether. The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (n-hexane/ethyl acetate = 5/1) to give compound I as a clear oil (60 mg, 95%). A solution of I (50 mg, mmol) in CH2Cl2 (1 ml) was added via syringe to a stirring solution of Grubbs second-generation catalyst (10.4 mg, mmol) in CH2Cl2 (3 ml). The flask was fitted with a condenser and refluxed under nitrogen for 9 h. The reaction mixture was purified on silica gel column, elutingwith hexane:ethylacetate (10:1) to afford the desired product (R)-5ae (25 mg, 54%). (R)-N-((2,4-dimethyl-1,4-dihydrocyclopenta[b]indol-1-yl)methyl)-N,4-dimethylbenzene sulfonamide: (R)-5ae White solid. 51% yield for two steps. 1 H NMR (500 MHz, CDCl3): 7.69 (d, J = 8.5 Hz, 2H), (m, 1H), 7.32 (d, J = 8.0 Hz, 2H), (m, 1H), (m, 2H), 6.47 (s, 1H), 3.76 (s, 3H), 3.63 (t, J = 7.5 Hz, 1H), 3.49 (dd, J = 13.0 and 6.5 Hz, 1H), 2.97 (dd, J = 13.0 and 8.5 Hz, 1H), 2.74 (s, 3H), 2.43 (s, 3H), 2.24 (d, J = 1.5 Hz, 3H). 13 C NMR (125 MHz, CDCl3): 151.3, 148.7, 143.4, 140.2, 134.0, 129.7, 127.6, 124.3, 119.7, 119.3, 118.4, 118.2, S26

27 117.7, 109.7, 52.6, 47.7, 36.9, 30.8, 21.5, HRMS (ESI) calcd for C22H24N2NaO2S [(M+Na + )]: , found: [α] 25 D = (c 0.25, CHCl3). 98% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 60/40, 0.8 ml/min. Retention times: 7.77 min (minor), 8.31 min (major). (R)-N-((2,4-dimethyl-1,3-dihydrobenzo[cd]indol-3-yl)methyl)-N,4-dimethylbenzenesulfonamide: (R)-6an Green solid. 57% yield for two steps. 1 H NMR (400 MHz, CDCl3): 7.63 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), (m, 2H), 6.92 (d, J = 1.2 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 3.75 (s, 3H), 3.27 (dd, J = 12.8 and 4.4 Hz, 1H), 3.09 (dd, J = 12.8 and 8.8 Hz, 1H), 2.68 (s, 3H), 2.42 (s, 3H), 2.00 (s, 3H). 13 C NMR (100 MHz, CDCl3): 143.3, 137.7, 134.3, 133.7, 129.6, 127.5, 127.3, 124.9, 124.7, 123.7, 122.8, 113.3, 112.2, 108.0, 55.6, 40.4, 36.7, 32.8, 22.9, HRMS (ESI) calcd for C23H26N2NaO2S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). Note: The ee value of (R)-6an can not be determined by HPLC analysis using a chiral stationary phase. The reaction was carried out following the procedure described above for synthesis of (R)-5ae. (2.0 equiv. NaH and 2.0 equiv. MeI were used) Procedure: To a stirred solution of the (R)-3aj (40 mg, 0.1 mmol), PPh3 (32 mg, 1.2 equiv) in anhydrous THF (2 ml) at 0 C was added DEAD (22 mg, 1.2 equiv). The mixture was allowed to warm to RT over 12 h until the substrate was consumed. Solvent was removed in a rotary evaporator, the resulting crude mixture was purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate (10:1) as the solvent to afford the desired product (R)-7aj (31 mg, 85%). (R)-9-methyl-4-(prop-1-en-2-yl)-2-tosyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole: (R)-7aj Yellow solid. 85% yield. 1 H NMR (400 MHz, CHCl3): 7.75 (d, J = 8.0 Hz, 2H), 7.44 (d, J = 7.6 Hz, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 5.2 Hz, 1H), 7.17 (t, J = 7.6 Hz, 1H), 7.04 (t, J = 7.6 Hz, 1H), 4.96 (s, 1H), 4.91 (s, 1H), 4.31 (s, 2H), (m, 1H), 3.61 (s, 3H), 3.47 (dd, J = 12.0 and 5.2 Hz, 1H), 3.28 (dd, J = 12.0 and 6.8 Hz, 1H), 2.42 (s, 3H), 1.69 (s, 3H). 13 C NMR (100 MHz, CHCl3): 144.7, 143.8, 137.3, 133.8, 130.7, 129.8, 127.6, 126.1, S27

28 121.4, 119.3, 119.1, 114.2, 108.8, 108.7, 48.7, 42.7, 41.5, 29.4, 21.5, HRMS (ESI) calcd for C22H24N2NaO2S [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). 97% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 80/20, 0.8 ml/min. Retention times: min (minor), min (major). (R)-6-methyl-4-(prop-1-en-2-yl)-2-tosyl-2,3,4,6-tetrahydro-1H-azepino[5,4,3-cd]indole: (R)-8ao White solid. 75% yield. Note: The reaction was carried out following the procedure described above for synthesis of (R)-7aj. (40 mg (R)-3ao was used). 1 H NMR (500 MHz, CDCl3): 7.72 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 7.5 Hz, 2H), (m, 2H), 6.88 (d, J =7.0 Hz, 1H), 6.78 (s, 1H), 5.16 (d, J =16.0 Hz, 1H), 5.04 (s, 1H), 4.96 (s, 1H), 4.33 (d, J =16.0 Hz, 1H), (m, 2H), 3.73 (s, 3H), 3.13 (dd, J = 13.0 and 11.0 Hz, 1H), 2.39 (s, 3H), 1.65 (s, 3H). 13 C NMR (125 MHz, CDCl3): 145.1, 143.0, 137.7, 136.9, 131.3, 129.6, 127.8, 127.0, 125.1, 121.2, 116.3, 114.9, 114.0, 107.9, 55.4, 55.2, 48.7, 32.8, 21.4, HRMS S28

29 (ESI) calcd for C22H24N2NaO2S [(M+Na + )]: , found: [α] 28 D = (c 1.0, CHCl3). 95% ee. HPLC analysis of the product: Daicel Chiralpak AD-3 column; hexane/2-propanol = 85/15, 0.8 ml/min. Retention times: min (major), min (minor). Procedure: To a stirred solution of indole 3ad (70 mg, 0.19 mmol) in dry DMF (2.0 ml), NaH (12.0 mg, 60% suspension in mineral oil, 0.29 mmol) was added portionwise under nitrogen atmosphere at 0 o C. The reaction mixture was then warmed to room temperature and stirred for 30 min. After cooling to 0 o C, Allyl bromide (37 mg, 0.30 mmol) was added dropwise to the reaction mixture. The reaction mixture was warmed to room temperature and stirred overnight. Water was added and the aqueous layer was extracted with ether. The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (n-hexane/ethyl acetate = 5/1) to give compound II as a clear oil (69 mg, 89%). A solution of II (68 mg, mmol) in CH2Cl2 (1 ml) was added via syringe to a stirring solution of Grubbs second-generation catalyst (0.017 mmol, 14.0 mg) in CH2Cl2 (10 ml). The reaction was stirred at 35 o C under nitrogen for 9 h. The reaction mixture was purified on silica gel column, elutingwith hexane:ethylacetate (10:1) to afford the desired product (R)-9ad (64 mg, 99%). (R)-N-allyl-4-methyl-N-(3-methyl-2-(1-methyl-1H-indol-3-yl)but-3-en-1-yl)benzenesulfonamide: (R)-II Colorless oil. 89% yield. 1 H NMR (500 MHz, CDCl3): 7.66 (d, J = 8.5 Hz, 2H), 7.56 (d, J = 8.0 Hz, 1H), 7.26 (d, J = 8.0 Hz, 1H), 7.24 (d, J = 8.0 Hz, 2H), (m, 1H), (m, 1H), 6.93 (s, 1H), (m, 1H), (m, 1H), 5.02 (s, 2H), (m, 1H), 3.97 (t, J = 8.0 Hz, 1H), 3.79 (dd, J = 16.5 and 7.5 Hz, 1H), 2.72 (s, 3H), (m, 1H), 3.66 (t, J = 7.5 Hz, 1H), 3.58 (dd, J = 13.5 and 6.5 Hz, 1H), 2.39 (s, 3H), 1.66 (s, 3H). 13 C NMR (125 MHz, CDCl3): 145.2, 143.0, 137.2, 137.0, 132.8, 129.5, 127.4, 127.1, 126.7, 121.5, 119.3, 118.8, 118.7, 113.2, 112.2, 109.1, 50.4, 48.9, 42.5, 32.6, 21.4, HRMS (ESI) calcd for S29

30 C24H28N2NaO2S [(M+Na + )]: , found: % ee. HPLC analysis of the product: Daicel Chiralpak IB column; hexane/2-propanol = 90/10, 0.8 ml/min. Retention times: 9.17 min (minor), 9.62 min (major). (R)-1-methyl-3-(4-methyl-1-tosyl-1,2,3,6-tetrahydropyridin-3-yl)-1H-indole: (R)-9ad White solid. 99% yield. 1 H NMR (400 MHz, CDCl3): 7.55 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.0 Hz, 1H), 7.27 (d, J = 8.0 Hz, 1H), (m, 1H), 7.20 (d, J = 8.0 Hz, 2H), 7.04 (t, J = 7.6 Hz, 1H), 6.90 (s, 1H), 5.50 (s, 1H), 3.71 (s, 3H), 3.67 (broad s, 3H), 3.40 (dd, J = 11.6 and 4.4 Hz, 1H), 3.24 (dd, J = 11.6 and 6.0 Hz, 1H), 2.36 (s, 3H), 1.57 (s, 3H). 13 C NMR (100 MHz, CDCl3): 143.2, 136.9, 136.0, 133.4, 129.4, , , 127.1, 121.4, 118.8, 118.6, 117.2, 113.5, 109.3, 49.3, 44.9, 37.3, 32.6, 21.5, HRMS (ESI) calcd for C22H24N2NaO2S [(M+Na + )]: , found: [α] 25 D = (c 1.0, CHCl3). 96% ee. HPLC analysis of the product: Daicel Chiralpak IA column; hexane/2-propanol = 80/20, 0.8 ml/min. Retention times: min (minor), min (major). Procedure: To a stirred solution of indole 3ad (133 mg, 0.36 mmol) and DMAP (176 mg, 1.44 mmol) in dry CH2Cl2 (4.0 ml) was added acetyl chloride (78 μl, 1.08 mmol) under nitrogen atmosphere at 0 o C. The reaction mixture was then warmed to room temperature and stirred at RT for 1 h. Water was added and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was S30

31 purified by column chromatography on silica gel (n-hexane/ethyl acetate = 5/1) to give compound III as a white solid (144 mg, 97%). To a stirred solution of III (37 mg, 0.1 mmol) in THF (1 ml) was added at -78 o C via a syringe a solution of sodium naphthalenide (2 ml, 0.5 M in THF, prepared by dissolving sodium (0.6 g, 26 mmol) and naphthalene (3.4 g, 26.5 mmol) in THF (52 ml) at 25 o C, until the dark green color remained). The reaction mixture was then stirred for 2 h at -78 o C, and aq. NH4Cl (2 ml) was added. It was extracted with EtOAc. The organic layer was dried over anhydrous Na2SO4. The solvent was removed and the residue was purified on silica gel column, elutingwith MeOH:CH2Cl2 (1:10) to afford the desired product (R)-10ad (22 mg, 86%). (R)-N-(3-methyl-2-(1-methyl-1H-indol-3-yl)but-3-en-1-yl)acetamide: (R)-10ad Colorless oil. 83% yield in two steps. 1 H NMR (500 MHz, CDCl3): 7.61 (d, J = 8.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H), (m, 1H), (m, 1H), 6.89 (s, 1H), 5.56 (broad s, 1H), 5.02 (s, 1H), 4.96 (s, 1H), 3.75 (s, 3H), (m, 3H), 1.92 (s, 3H), 1.65 (s, 3H). 13 C NMR (125 MHz, CDCl3): 170.0, 145.6, 137.2, 127.4, 126.2, 121.7, 119.4, 118.9, 113.5, 111.8, 109.2, 43.8, 41.4, 32.7, 23.3, HRMS (ESI) calcd for C16H20N2NaO [(M+Na + )]: , found: [α] 27 D = (c 0.5, CHCl3). Note: The ee value of (R)-10ad can not be determined by HPLC analysis using a chiral stationary phase. Procedure: (R)-3ca (39 mg, 0.1 mmol) was dissolved into 2 ml anhydrous CH3CN in an oven-dried 10 ml flask containing a stir bar under Ar atmosphere. K2CO3 (80 mg, 5.0 equiv) was added and the resulting solution was stirring for 5 minutes. After that, PhSH (45 μl, 4.0 equiv) was added via syringe and the mixture was heated to 35 o C for 9 h until the substrate was consumed. Solvent was removed in a rotary evaporator, the resulting crude mixture was purified by flash column chromatography on silica gel with DCM/MeOH (10:1) as the solvent to afford the desired product (R)-12ca (26 mg, 93%). (R)-2-(2-methyl-1H-indol-3-yl)but-3-en-1-amine: (R)-12ca Yellow solid. 93% yield. 1 H NMR (500 MHz, CDCl3): 7.46 (t, J = 8.5 Hz, 2H), (m, 1H), (m, 1H), 7.01 (s, 1H), (m, 1H), 5.17 (d, J = 11.0 Hz, 1H), 5.09 (d, J = 17.5 Hz, 1H), (m, 1H), (m, 2H), 1.97 (s, 3H). 13 C NMR (125 MHz, CDCl3): 136.3, 136.0, 135.1, 126.7, 120.2, 119.1, 118.7, 116.5, 111.1, 105.8, 42.5, 38.4, HRMS (ESI) calcd for C13H16N2Na [(M+Na + )]: , found: [α] 28 D = (c 1.0, CHCl3). Note: The ee value of (R)-12ca can not be determined by HPLC analysis using a chiral stationary phase. S31

32 (R)-6-methyl-4-vinyl-2,3,4,6-tetrahydro-1H-azepino[5,4,3-cd]indol-1-one: (R)-11ct Colorless oil. 35% yield. Note: The reaction was carried out following the procedure described above for synthesis of (R)-12ca (44.3 mg (R)-3ct was used). 1 H NMR (500 MHz, CDCl3): (m, 1H), (m, 1H), (m, 1H), 6.90 (s, 1H), 6.63 (broad s, 1H), 5.92 (broad s, 1H), (m, 2H), 3.80 (s, 3H), 3.80 (broad s, 1H), 3.58 (broad s, 2H). 13 C NMR (125 MHz, CDCl3): 171.2, 137.4, 127.6, 124.8, 124.1, 123.3, 121.5, 116.6, 113.1, 48.0, 32.9, HRMS (ESI) calcd for C14H14N2NaO [(M+Na + )]: , found: [α] 26 D = (c 1.0, CHCl3). 90% ee. HPLC analysis of the product: Daicel Chiralpak IB column; hexane/2-propanol = 80/20, 0.8 ml/min. Retention times: 6.14 min (major), min (minor). (R)-6-methoxy-9-methyl-4-vinyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indol-1-one: (R)-13cl White solid. 70% yield. Note: The reaction was carried out following the procedure described above for synthesis of (R)-12ca (49 mg (R)-3cl was used). 1 H NMR (500 MHz, CDCl3): (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 2H), 4.10 (s, 3H), (m, 1H), 3.84 (s, 3H), (m, 1H), (m, 1H). 13 C NMR (125 MHz, CDCl3): 162.9, 154.3, 137.4, 134.7, 125.7, 124.2, 120.2, 117.0, 116.1, 111.2, 101.2, 55.8, 47.2, 37.5, HRMS (ESI) calcd for S32