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1 Supporting Information Access to Hexahydrocarbazoles: The Thorpe Ingold Effects of the Ligand on Enantioselectivity Hao Chen, Lijia Wang, Feng Wang, Liu-Peng Zhao, Pan Wang, and Yong Tang* anie_ _sm_miscellaneous_information.pdf

2 Contents 1. General Information... S2 2. Reaction Optimizations... S3 3. Synthesis of Ligands... S9 4. General Procedure... S10 5. Experimental procedure for the scale-up reaction... S28 6. Experimental procedure for transformation of rac-3bu and 3br.... S29 7. Copies of NMR Spectra... S33 8. Copies of HPLC Data... S75 9. X-ray Data... S100 S1

3 1. General Information Unless stated otherwise, all reactions were carried out under an atmosphere of nitrogen using standard Schlenk techniques. All solvents and reagents were obtained from commercial sources and were purified according to standard procedures before use. 1 H NMR spectra were recorded on a Varian Mercury 400 MHz or Agilent Mercury 400 MHz spectrometer in chloroform-d. All signals were reported in ppm with the internal TMS signal at 0.00 ppm as a standard. Data for 1 H NMR were recorded as follows: chemical shift (δ, ppm), multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet or unresolved, coupling constant(s) in Hz, integration). 13 C NMR spectra were recorded on a Varian Mercury 100 MHz or Agilent Mercury 100 MHz spectrometer in chloroform-d. All signals were reported in ppm with the internal chloroform signal at 77.0 ppm as a standard. 19 F NMR spectra were recorded on a Varian Mercury 375 MHz or Agilent Mercury 375 MHz spectrometer in chloroform-d. IR spectra were recorded on a Perkin Elmer 983, Digital FT IR spectrometer; frequencies are given in reciprocal centimeters (cm -1 ) and only selected absorbance is reported. High resolution mass spectra were recorded on an Agilent 6224 TOF LC/MS (ESI) mass spectrometer. S2

4 2. Reaction Optimizations Racemic reaction: Table S1 The effect of Lewis acid a. Entry Lewis acid t (h) Yield (%) b 1 Sc(OTf) Zn(OTf) Yb(OTf) Ni(OTf) Fe(OTf) Fe(OTf) Cu(OTf) Cu(NTf2) Cu(OAc)2 24 NR 10 CuBr2 24 NR 11 Cu(ClO4)2. 6H2O Ni(ClO4)2. 6H2O Mg(ClO4)2. 6H2O 24 NR 14 Co(ClO4)2. 6H2O a 1a (0.2 mmol), 2a (0.8 mmol), Lewis acid (0.02 mmol), DCM (2.0 ml), 30 o C. b Isolated yield. Table S2 The effect of Solvent a. Entry Solvent t (h) Yield (%) b S3

5 1 CH3CN 24 NR 2 CH3CO2Et 24 NR 3 THF PhCH PhCF PhF CHCl DCE DCM 5 87 a 1a (0.2 mmol), 2a (0.8 mmol), Cu(OTf) 2 (0.02 mmol), Solvent (2.0 ml), 30 o C. b Isolated yield. Table S3 The Optimization Studies a. Entry 1a/2a T ( o C) t (h) Yield (%) b 1 1/ / / a 1a (0.2 mmol), Cu(OTf) 2 (0.02 mmol), DCM(2.0 ml). b Isolated yield. Enantioselective reaction: Table S4 Effect of ester groups on the annulation reactions a. Entry R t (h) Yield (%) b ee (%) d 1 Me (3ba) Et (3br) S4

6 3 c i Pr (3bs) 10 / / a Reaction conditions: 1b (0.2 mmol), 2a-c (0.6 mmol), Cu(OTf) 2 (0.02 mmol), L4 (0.024 mmol), DCM (3.0 ml), 30 o C. b Isolated yield. c Friedel Crafts product was observed. d Determined by Chiral HPLC. Table S5 The effects of N-substituents of indole a. Entry R t (h) Yield (%) b ee (%) c 1 Me(3ba) Bn(3aa) allyl(3ca) PhOCO(3da) 24 NR / a Reaction conditions: 1 (0.2 mmol), 2a (0.6 mmol), Cu(OTf) 2 (0.02 mmol), L4 (0.024 mmol), DCM (3.0 ml), 30 o C. b Isolated yield. c Determined by Chiral HPLC. Table S6 Effect of ligands on the annulation reactions a. Entry L Yield (%) b ee (%) d 1 L S5

7 2 L L L c L8 3 / 6 c L9 3 / 7 L c L11 5 / 9 c L12 6 / 10 c L13 7 / 11 L14 64 (-)43 a Reaction conditions: 1b (0.2 mmol), 2a (0.6 mmol), Cu(OTf) 2 (0.02 mmol), L (0.024 mmol), DCM (3.0 ml), 30 o C. b Isolated yield. c Determined by 1 H NMR spectroscopy. d Determined by Chiral HPLC. Table S7 Effect of Lewis acid on the annulation reactions a. Entry Lewis acid Yield (%) b ee (%) d 1 Cu(OTf) c Cu(BAr F )2 / / 3 c Cu(PF6)2 / / 4 Cu(SbF6) Cu(NTf2) Cu(ClO4)2. 6H2O Fe(OTf)3 trace / 8 Fe(OTf)2 trace / 9 Ni(OTf)2 trace / 10 Zn(OTf)2 trace / 11 Zn(ClO4)2. 6H2O 27 (-)11 S6

8 12 Ni(ClO4)2. 6H2O trace / 13 Mg(ClO4)2. 6H2O trace / 14 Co(ClO4)2. 6H2O trace / 15 Fe(ClO4)2. 6H2O trace / a Reaction conditions: 1b (0.2 mmol), 2a (0.6 mmol), Lewis acid (0.02 mmol), L2 (0.024 mmol), DCM (3.0 ml), 30 o C. b Isolated yield. c Friedel Crafts product was observed. d Determined by Chiral HPLC. Table S8 Effect of solvents on the annulation reactions a. Entry Solvent Yield (%) b ee (%) c 1 DCM DCE CHCl CH3CCl CH2ClCHCl TTCE PhCH PhCF PhCl PhF THF ,4-dioxane CH3CN NR / 14 DME DMF trace / a Reaction conditions: 1b (0.2 mmol), 2a (0.6 mmol), Cu(OTf) 2 (0.02 mmol), L2 (0.024 mmol), Solvent (3.0 ml), 30 o C. b Isolated yield. c Determined by Chiral HPLC. S7

9 Table S9 Optimization of the enantioselective reaction conditions a. Entry L X (mol %) T ( o C) V (ml) t (h) Yield (%) b ee (%) c 1 L L L L L L L Wing-BOX Wing-BOX Wing-BOX Wing-BOX Wing-BOX Wing-BOX Wing-BOX Wing-BOX Wing-BOX Wing-BOX Wing-BOX d Wing-BOX e Wing-BOX f Wing-BOX g Wing-BOX a Reaction conditions: 1b (0.2 mmol), 2a (0.6 mmol), Cu(OTf) 2 (0.02 mmol), L (0.024 mmol). b Isolated yield. c Determined by Chiral HPLC. d 5 mol% catalyst was employed, DCM (3 ml). e 1b (0.5 mmol), 2a (1.5 mmol), Cu(OTf) 2 (0.01 mmol), L (0.012 mmol), DCM (3 ml). f 1b (1.0 mmol), 2a (3.0 mmol), Cu(OTf) 2 (0.01 mmol), L (0.012 mmol), DCM (3 ml). g 1b (2.0 mmol), 2a (6.0 mmol), Cu(OTf) 2 (0.01 mmol), L (0.012 mmol), DCM (3 ml). S8

10 3. Synthesis of Ligands NaH (2.0 mmol, 60 % dispersion in mineral oil) was added to a solution of A (0.5 mmol) in anhydrous THF (2 ml) at room temperature under N2 atmosphere. The mixture was stirred at room temperature for 30 min and B (4.0 mmol) was slowly added. The resulting suspension was allowed to stir at 70 o C and monitored by TLC, until the complete consumption of A. The reaction mixture was filtered through a thin layer of celite and eluted with DCM and EA. The solvent was removed by reduced pressure and the residue was purified by flash chromatography over silica gel (EA/petroleum ether, 1/10) as eluent to afford the product. White solid (47.9 mg, 25% yield); [a]d 26 = (c 1.00, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 10H), 5.28 (t, J = 9.4 Hz, 2H), 4.67 (dd, J1 = 10.4 Hz, J2 = 8.8 Hz, 2H), 4.09 (t, J = 8.4 Hz, 2H), (m, 2H), 1.10 (dd, J1 = 14.8 Hz, J2 = 6.4 Hz, 12H). 13 C NMR (100 MHz, CDCl3): δ 167.0, 142.4, 128.6, 127.4, 126.9, 74.2, 69.5, 54.9, 31.5, 18.8, 18.7; IR (neat): 2973, 2893, 1642, 1494, 1454, 1388, 1348, 1266, 1229, 1146, 1087, 988, 964, 933, 861, 760, 702, 613 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C25H31N2O2 + [M+H] + : ; found: Colorless oil (91.8 mg, 41% yield); [α]d 26 = (c 0.99, CHCl3); 1 H NMR (400 MHz, S9

11 CDCl3) δ (m, 10H), 5.25 (dd, J1 = 10.4 Hz, J2 = 8.8 Hz, 2H), 4.63 (dd, J1 = 10.4 Hz, J2 = 8.4 Hz, 2H), (m, 2H), (m, 4H), (m, 12H); 13 C NMR (100 MHz, CDCl3) δ 167.7, 142.5, 128.5, 127.4, 126.8, 74.4, 69.5, 52.8, 45.0, 28.3, 28.0, 25.4; IR (neat): 2950, 2867, 1643, 1494, 1452, 1351, 1262, 1221, 1154, 996, 956, 756, 698 cm -1 ; HRMS-ESI: Exact mass calcd for C29H35N2O2 + [M+H] + : , found: General Procedure Racemic reaction: A mixture of Cu(OTf)2 (0.03 mmol) and indole 1 (0.3 mmol) was stirred at 0 o C, the solution of 2a (0.9 mmol) in DCM (2.0 ml) was then added dropwise to the system. When the reaction was completed (monitored by TLC), the reaction mixture was filtered through a thin layer of silica gel and eluted with CH2Cl2. The solvent was removed by reduced pressure and the residue was purified by flash chromatography over silica gel (EA/petroleum ether, 1/5-1/2) to afford the product. Table S10. Substrate scope of the racemic tandem cyclization reaction. a S10

12 White foam (95% yield); 1 H NMR (400 MHz, CDCl3): δ 6.89 (d, J =7.2 Hz, 1H), 6.72 (t, J = 7.2 Hz, 1H), 6.61 (d, J = 6.8 Hz, 1H), 4.13 (d, J = 1.6 Hz, 1H), 3.79 (s, 3H), (m, 6H), 3.42 (s, 3H), 2.86 (s, 3H), (m, 4H), 2.21 (s, 3H), 1.44 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.1, 171.3, 170.9, 169.0, 151.8, 137.3, 130.4, 123.8, 121.2, 120.3, 75.8, 58.3, 52.8, 52.7, 52.5, 52.3, 51.6, 44.5, 43.6, 34.7, 33.4, 27.0, 18.3; IR (neat): 2958, 1758, 1733, 1593, 1472, 1449, 1432, 1257, 1233, 1208, 1173, 1160, 1120, 1075, 1043, 1016, 986, 932, 854, 830, 786, 753, 678, 647 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C23H30NO8 + [M+H] + : ; Found: S11

13 White foam (98% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), 6.56 (dd, J1 = 8.4 Hz, J2 = 2.4 Hz, 1H), 6.39 (d, J = 8.8 Hz, 1H), 6.31 (d, J = 2.8 Hz, 1H), 4.50 (ABd, J = 15.6 Hz, 1H), 4.37 (d, J = 2.0 Hz, 1H), 3.99 (ABd, J = 15.6 Hz, 1H), (m, 9H), 3.52 (s, 3H), 3.43 (s, 3H), 3.03 (d, J = 16.0 Hz, 1H), 2.63 (dd, J = 15.6, 1.6 Hz, 1H), 2.47 (ABd, J = 15.6 Hz, 1H), 2.34 (ABd, J = 15.6 Hz, 1H), 1.08 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 172.1, 171.3, 170.7, 169.1, 153.8, 146.1, 138.8, 137.3, 128.3, 127.8, 127.1, 112.9, 112.1, 109.4, 72.7, 58.3, 58.0, 55.6, 52.9, 52.7, 52.6, 52.5, 51.7, 44.6, 35.1, 31.9, 26.9; IR (neat): 2954, 1734, 1492, 1434, 1240, 1208, 1112, 1036, 943, 848, 818, 744, 702, 646 cm -1 ; HRMS-ESI: Exact mass calcd for C29H34NO9 + [M+H] + : ; Found: White foam (93% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), 6.82 (dd, J = 8.0, 0.8 Hz, 1H), 6.52 (d, J = 1.2 Hz, 1H), 6.39 (d, J = 8.0 Hz, 1H), 4.54 (ABd, J = 16.0 Hz, 1H), 4.38 (d, J = 2.0 Hz, 1H), 4.00 (ABd, J = 16.0 Hz, 1H), (m, 6H), 3.48 (s, 3H), 3.41 (s, 3H), 3.06 (d, J = 15.6 Hz, 1H), 2.62 (dd, J = 16.0, 2.0 Hz, 1H), 2.49 (ABd, J = 16.0 Hz, 1H), 2.32 (ABd, J = 15.6 Hz, 1H), 2.20 (s, 3H), 1.10 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 172.2, 171.3, 170.6, 169.1, 150.0, 138.8, 135.6, 128.9, 128.3, 128.2, 127.7, 127.0, 123.2, 110.9, 72.4, 57.8, 57.2, 52.9, 52.6, 52.5, 51.7, 44.4, 35.1, 32.1, 26.9, 20.8; IR (neat): 2954, 1749, 1724, 1619, 1497, 1433, 1262, 1234, 1193, 1159, 1059, 1021, 961, 856, 803, 762, 705, 643 cm -1 ; HRMS-ESI: Exact mass calcd for C29H34NO8 + [M+H] + : ; Found: S12

14 White foam (91% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), (m, 1H), 6.41 (s, 2H), 4.52 (ABd, J = 15.6 Hz, 1H), 4.41 (s, 1H), 3.99 (ABd, J = 16.0 Hz, 1H), (m, 6H), (m, 6H), 3.03 (d, J = 16.0 Hz, 1H), 2.64 (d, J = 16.0 Hz, 1H), (m, 2H), 1.06 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ171.9, 171.2, 170.5, 168.9, (J = Hz), 148.1, 138.2, (J = 7.1 Hz), 128.4, 127.7, 127.2, (J = 23.0 Hz), (J = 8.3 Hz), (J = 23.4 Hz), 72.3, 57.7, 57.4, 52.9, 52.8, 52.6(3), 52.5(6), 51.5, 44.5, 34.9, 31.7, 26.9; 19 F NMR (375 MHz, CDCl3): ; IR (neat): 2954, 1750, 1723, 1492, 1434, 1269, 1233, 1185, 1117, 1094, 1021, 960, 877, 857, 805, 762, 702, 642 cm -1 ; HRMS-ESI: Exact mass calcd for C28H31FNO8 + [M+H] + : ; Found: White foam (83% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 3H), (m, 3H), 6.70 (t, J = 7.6 Hz, 1H), 6.46 (d, J = 7.2 Hz, 1H), 4.62 (ABd, J = 15.2 Hz, 1H), 4.32 (d, J = 2.0 Hz, 1H), 3.85 (s, 3H), 3.75 (ABd, J = 14.8 Hz, 1H), 3.65 (s, 3H), 3.62 (s, 3H), 3.39 (s, 3H), 2.74 (d, J = 15.6 Hz, 1H), 2.51 (dd, J = 15.6, 2.0 Hz, 1H), 2.40 (s, 3H), (m, 2H), 0.44 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 172.1, 171.1, 170.9, 169.2, 149.4, 137.9, 137.4, 130.4, 129.5, 128.2, 127.6, 123.0, 120.9, 120.4, 69.1, 58.1, 54.7, 52.8, 52.6, 52.4(4), 52.4(2), 51.5, 43.9, 35.4, 29.4, 27.1, 19.2; IR (neat): 2952, 2920, 1733, 1434, 1257, 1218, 1117, 1071, 1020, 971, 854, 786, 758, 745, 702 cm -1 ; HRMS-ESI: Exact mass calcd for C29H34NO8 + [M+H] + : ; Found: S13

15 White foam (78% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 3H), (m, 2H), 6.70 (d, J = 4.4 Hz, 2H), 6.27 (t, J = 4.2 Hz, 1H), 5.06 (ABd, J = 14.8 Hz, 1H), 4.34 (s, 1H), 3.89 (s, 3H), 3.84 (s, 3H), (m, 7H), 3.40 (s, 3H), 2.87 (d, J = 16.0 Hz, 1H), 2.54 (d, J = 15.6, 1H), (m, 2H), 0.52 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 172.1, 171.2, 170.8, 169.2, 147.1, 139.0, 138.4, 137.8, 129.5, 128.1, 127.3, 120.9, 115.6, 111.9, 69.1, 57.7, 55.6, 53.3, 52.8, 52.6, 52.5, 52.4, 51.6, 44.4, 35.0, 30.0, 27.1; IR (neat): 2953, 1735, 1603, 1487, 1433, 1248, 1220, 1116, 1074, 958, 854, 785, 748, 702 cm -1 ; HRMS-ESI: Exact mass calcd for C29H34NO9 + [M+H] + : ; Found: White foam (85% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 4H), 7.03 (d, J = 7.6 Hz, 2H), (m, 1H), (m, 4H), 6.08 (d, J = 7.6 Hz, 1H), 4.52 (d, J = 2.0 Hz, 1H), (m, 7H), 3.45 (s, 3H), 3.15 (s, 3H), 3.01 (d, J = 15.6 Hz, 1H), (m, 5H), 2.57 (ABd, J = 16.0 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 172.2, 171.4, 170.8, 168.6, 154.2, 139.8, 136.6, 132.9, 130.5, 128.7, 128.1, 127.6, 126.7, 126.5, 126.4, 123.3, 119.3, 111.2, 70.8, 58.1, 58.0, 53.0, 52.8, 52.6, 52.5, 51.6, 49.7, 49.5, 34.4, 27.5; IR (neat): 2947, 1742, 1721, 1601, 1485, 1432, 1251, 1109, 1052, 964, 847, 760, 743, 726, 702, 612 cm -1 ; HRMS-ESI: Exact mass calcd for C34H36NO8 + [M+H] + : ; Found: S14

16 White foam (93% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), (m, 1H), 6.72 (d, J = 7.4 Hz, 1H), 6.64 (t, J = 7.4 Hz, 1H), 6.49 (d, J = 8.0 Hz, 1H), 5.10 (s, 2H), (m, 1H), 4.29 (s, 1H), 3.77 (s, 3H), (m, 7H), 3.40 (s, 3H), 3.12 (dd, J = 13.2, 3.2 Hz, 1H), 2.90 (d, J = 16.0 Hz, 1H), 2.71 (s, 3H), (m, 3H); 13 C NMR (100 MHz, CDCl3) δ 171.8, 171.1, 170.6, 168.8, 156.5, 153.4, 136.5, 129.9, 129.3, 128.3, 128.0, 127.9, 122.9, 118.5, 109.9, 70.5, 66.6, 57.0, 52.9, 52.8, 52.7, 52.6, 51.7, 51.1, 48.7, 38.9, 30.9, 27.1; HRMS-ESI: Exact mass calcd for C30H35N2O10 + [M+H] + : ; Found: White foam (74% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), (m, 1H), (m, 2H), 6.44 (d, J = 7.6 Hz, 1H), 5.02 (s, 2H), 4.59 (s, 1H), 4.29 (s, 1H), 3.77 (s, 3H), (m, 6H), 3.39 (s, 3H), (m, 1H), 2.93 (d, J = 15.6 Hz, 1H), (m, 4H), (m, 3H), (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 171.9, 171.2, 170.5, 169.0, 156.0, 152.7, 136.5, 130.9, 128.9, 128.3, 127.9, 127.8, 122.8, 118.3, 109.0, 71.9, 66.3, 57.0, 52.9, 52.7, 52.6, 52.5, 51.3, 46.9, 43.4, 38.1, 36.7, 34.2, 26.8; IR (neat): 2952, 1733, 1603, 1492, 1433, 1237, 1115, 994, 854, 746, 698 cm -1 ; HRMS-ESI: Exact mass calcd for C31H37N2O10 + [M+H] + : ; Found: White foam (91% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), 6.98 (t, J S15

17 = 7.4 Hz, 1H), (m, 2H), 6.38 (d, J = 8.0 Hz, 1H), (m, 1H), (m, 2H), (m, 2H), 4.08 (ABd, J = 16.4 Hz, 1H), (m, 6H), 3.43 (s, 3H), 3.29 (s, 3H), 3.09 (d, J = 15.6 Hz, 1H), 2.69 (d, J = 15.6 Hz, 1H), 2.59 (ABd, J = 16.0 Hz, 1H), 2.38 (ABd, J = 16.0 Hz, 1H), (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 172.1, 171.3, 170.4, 168.8, 153.3, 139.2, 133.4, 132.8, 128.5, 128.3, 127.1, 126.8, 123.0, 118.9, 118.7, 110.4, 71.0, 57.8(1), 57.7(9), 52.9, 52.8, 52.5, 51.5, 48.3, 48.1, 34.1, 27.2; IR (neat): 2956, 1733, 1598, 1484, 1242, 1178, 1109, 1032, 963, 910, 850, 748, 699, 635 cm -1 ; HRMS-ESI: Exact mass calcd for C30H34NO8 + [M+H] + : ; Found: White foam (90% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), 6.78 (d, J = 8.0 Hz, 1H), 6.53 (s, 1H), 6.26 (d, J = 8.0 Hz, 1H), (m, 1H), (m, 2H), (m, 2H), 4.06 (ABd, J = 16.4 Hz, 1H), (m, 6H), 3.43 (s, 3H), 3.27 (s, 3H), 3.09 (d, J = 16.0 Hz, 1H), 2.68 (dd, J1 = 15.6 Hz, J2 = 2.0 Hz, 1H), 2.56 (ABd, J = 15.6 Hz, 1H), 2.37 (ABd, J = 16.0 Hz, 1H), (m, 5H); 13 C NMR (100 MHz, CDCl3) δ172.2, 171.3, 170.5, 168.9, 151.3, 139.6, 133.7, 133.1, 129.1, 128.3, 128.2, 127.1, 126.7, 123.6, 118.6, 110.5, 71.4, 58.5, 58.0, 52.9, 52.6, 52.5, 51.6, 48.4, 48.1, 34.2, 27.3, 20.8; IR (neat): 2956, 1751, 1722, 1496, 1432, 1262, 1229, 1116, 1021, 958, 918, 852, 819, 763, 706, 643 cm -1 ; HRMS-ESI: Exact mass calcd for C31H36NO8 + [M+H] + : ; Found: White foam (93% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), 6.52 (dd, J = 8.4, 2.4 Hz, 1H), 6.34 (d, J = 2.4 Hz, 1H), 6.25 (d, J = 8.4 Hz, 1H), (m, 1H), (m, 2H), 4.46 (d, J = 2.0 Hz, 1H), 4.39 (ABd, J = 16.4 Hz, 1H), 4.05 S16

18 (ABd, J = 16.0 Hz, 1H), (m, 9H), 3.45 (s, 3H), 3.31 (s, 3H), 3.08 (d, J = 16.0 Hz, 1H), 2.69 (dd, J = 15.6, 2.0 Hz, 1H), 2.55 (ABd, J = 16.0 Hz, 1H), 2.39 (ABd, J = 16.0 Hz, 1H), (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 172.1, 171.3, 170.6, 168.8, 153.7, 147.5, 139.6, 134.8, 133.6, 128.3, 127.2, 126.7, 118.8, 112.9, 111.5, 109.9, 71.9, 59.5, 58.1, 55.6, 52.9, 52.7, 52.5, 51.5, 48.4, 48.2, 34.2, 27.3; IR (neat): 2953, 1727, 1496, 1433, 1249, 1216, 1113, 1042, 970, 919, 852, 813, 776, 757, 736, 698 cm - 1 ; HRMS-ESI: Exact mass calcd for C31H36NO9 + [M+H] + : ; Found: White foam (94% yield); 1 H NMR (400 MHz, CDCl3) δ (m, 4H), (m, 1H), (m, 2H), 6.59 (td, J = 7.2, 0.8 Hz, 1H), 5.97 (d, J = 8.0 Hz, 1H), 4.39 (ABd, J = 17.2 Hz, 1H), 4.09 (ABd, J = 17.2 Hz, 1H), (m, 4H), 3.62 (s, 3H), 3.36 (s, 3H), 3.21 (s, 3H), (m, 1H), 2.77 (ABd, J = 15.2 Hz, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H); 13 C NMR (100 MHz, CDCl3) δ 172.6, 171.5, 170.7, 170.0, 152.6, 138.8, 133.3, 128.3, 128.1, 126.5, 126.3, 122.5, 117.7, 107.8, 81.2, 59.3, 57.1, 52.9, 52.8, 52.4, 52.2, 52.1, 51.0, 44.8, 36.4, 32.8, 31.0, 23.0; IR (neat): 2955, 1732, 1491, 1432, 1351, 1223, 1200, 1161, 1089, 986, 946, 913, 878, 834, 749, 733, 696, 634 cm -1 ; HRMS-ESI: Exact mass calcd for C30H34NO8 + [M+H] + : ; Found: Enantioselective reaction: A mixture of Cu(OTf)2 (0.01 mmol) and phenyl bisoxazoline (Wing-BOX, mmol) in DCM (2 ml) was stirred at 30 o C for 2 h under nitrogen. Then, the system was cooled to -78 o C, the indole 1 (1.0 mmol) was added to the catalyst solution and S17

19 0.5 ml DCM was added to wash the tube wall, the solution of 2a (3.0 mmol) in DCM (0.5 ml) was then added dropwise to the system. When the reaction was completed (monitored by TLC), the reaction mixture was filtered through a thin layer of silica gel and eluted with CH2Cl2. The solvent was removed by reduced pressure and the residue was purified by flash chromatography over silica gel (EA/petroleum ether, 1/5-1/2) to afford the product. 3br: A mixture of Cu(OTf)2 (0.01 mmol) and phenyl bisoxazoline (Wing-BOX, mmol) in DCM (6 ml) was stirred at 30 o C for 2 h under nitrogen. Then, the system was cooled to -78 o C, the solution of 1r (0.1 mmol) in DCM (0.5 ml) and the solution of 2a (0.3 mmol) in DCM (0.5 ml) was added dropwise to the system at the same time. When the reaction was completed (monitored by TLC), the reaction mixture was filtered through a thin layer of silica gel and eluted with CH2Cl2. The solvent was removed by reduced pressure and the residue was purified by flash chromatography over silica gel (EA/petroleum ether, 1/5) to afford the product 3br. White foam (99% yield, 96% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 10/90, 0.80 ml/min, λ = 268 nm: tr (major) = 12.4 min, tr (minor) = 13.7 min.); [α]d 28 = (c 1.00, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 7.07 (dt, J = 8.0, 1.2 Hz, 1H), (m, 1H), 6.63 (t, J = 7.4 Hz, 1H), 6.49 (d, J = 8.0 Hz, 1H), 4.19 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), (m, 6H), 3.39 (s, 3H), 2.93 (d, J = 16.0 Hz, 1H), 2.81 (s, 3H), (m, 2H), 2.37 (ABd, J = 15.6 Hz, 1H), 1.38 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.2, 171.3, 170.7, 169.3, 152.5, 134.7, 128.4, 122.5, 118.2, 109.4, 74.7, 57.4, 52.9, 52.8, 52.6, 52.5, 51.7, 44.5, 39.4, 35.0, 33.3, 26.8; IR (neat): 2958, 1747, 1726, 1607, 1493, 1467, 1450, 1432, 1271, 1241, 1210, 1195, 1172, 1160, 1111, 1080, 987, 957, 931, 850, 743, 643, 623 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H28NO8 + [M+H] + : ; Found: S18

20 White foam (98% yield, 98% ee, >99/1 dr); (Chiralcel IF, i-proh/co2 = 10/90, 1.30 ml/min, λ = 230 nm: tr (minor) = 8.7 min, tr (major) = 9.6 min.); [α]d 30 = (c 1.00, CHCl3); 1 H NMR (400 MHz, CDCl3): δ (m, 1H), (m, 2H), 4.21 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), (m, 6H), 3.50 (s, 3H), 3.03 (d, J = 16.0 Hz, 1H), (m, 4H), 2.55 (dd, J = 16.0, 2.4 Hz, 1H), 2.29 (ABd, J = 16.4 Hz, 1H), 1.50 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.1, 170.9, 170.5, 169.2, (J = Hz), (J = 9.2 Hz), (J = 9.3 Hz), (J = 16.9 Hz), (J = 21.1 Hz), (J = 2.6 Hz), 75.0, 57.1, 52.8, 52.7(3), 52.7(0), 52.6, 51.5, 44.5, 38.9, 33.3, 30.7, 26.7; 19 F NMR (375 MHz, CDCl3): ; IR (neat): 2957, 1738, 1619, 1434, 1241, 1101, 1069, 1009, 964, 855, 827, 781, 733 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27FNO8 + [M+H] + : ; Found: White foam (94% yield, 97% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 254 nm: tr (major) = 21.2 min, tr (minor) = 30.3 min.); [α]d 29 = (c 1.00, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 7.00 (t, J = 8.0 Hz, 1H), 6.53 (dd, J = 8.0, 0.8 Hz, 1H), 6.36 (dd, J = 7.6, 0.4 Hz, 1H), 4.23 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), 3.69(3)-3.68(6) (m, 6H), 3.51 (s, 3H), 3.15 (d, J = 16.4 Hz, 1H), 3.05 (ABd, J = 16.0 Hz, 1H), 2.78 (s, 3H), 2.54 (dd, J = 16.0, 2.4 Hz, 1H), 2.20 (ABd, J = 16.4 Hz, 1H), 1.57 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.3, 170.7, 170.5, 169.2, 154.5, 129.9, 129.8, 129.7, 119.6, 107.7, 75.3, 57.2, 52.8(0), 52.7(5), 52.6, 51.4, 46.1, 39.1, 31.7, 29.5, 26.6; IR (neat): 2953, 1735, 1596, 1432, 1245, 1124, 1070, 1047, 1001, 909, 848, 775, 741 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27ClNO8 + [M+H] + : ; Found: S19

21 White foam (96% yield, >99% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 226 nm: tr (major) = 19.1 min, tr (minor) = 25.3 min.); [α]d 29 = +7.0 (c 0.98, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 6.92 (t, J = 7.8 Hz, 1H), (m, 1H), 6.40 (d, J = 7.6 Hz, 1H), 4.24 (d, J = 2.4 Hz, 1H), 3.78 (s, 3H), 3.69(2)-3.68(5) (m, 6H), 3.51 (s, 3H), 3.24 (d, J = 16.0 Hz, 1H), 3.06 (ABd, J = 16.0 Hz, 1H), 2.78 (s, 3H), 2.54 (dd, J = 16.0, 2.0 Hz, 1H), 2.14 (ABd, J = 16.0 Hz, 1H), 1.59 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.4, 170.6, 170.5, 169.3, 154.8, 131.1, 130.0, 123.0, 118.5, 108.3, 75.6, 57.2, 52.8(1), 52.7(8), 52.6(4), 52.5(9), 51.3, 46.7, 39.1, 31.5, 29.5, 26.7; IR (neat): 2953, 1725, 1593, 1569, 1469, 1438, 1426, 1273, 1235, 1202, 1119, 1069, 1044, 1019, 994, 961, 932, 911, 857, 829, 769, 756, 731, 693, 642 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27BrNO8 + [M+H] + : ; Found: White foam (99% yield, 96% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 315 nm: tr (major) = 12.9 min, tr (minor) = 16.4 min.); [α]d 28 = (c 0.99, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 6.88 (dd, J = 8.0, 1.2 Hz, 1H), 6.54 (d, J = 0.8 Hz, 1H), 6.42 (d, J = 8.0 Hz, 1H), 4.14 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), (m, 6H), 3.39 (s, 3H), 2.93 (d, J = 16.0 Hz, 1H), 2.78 (s, 3H), (m, 2H), 2.36 (ABd, J = 16.0 Hz, 1H), 2.20 (s, 3H), 1.37 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.2, 171.3, 170.7, 169.3, 150.6, 135.0, 128.9, 127.6, 123.2, 109.8, 75.0, 57.5, 52.8, 52.6, 52.5(4), 52.4(8), 51.7, 44.5, 40.3, 35.0, 33.4, 26.8, 20.7; IR (neat): 2954, 1744, 1732, 1714, 1617, 1501, 1457, 1257, 1243, 1214, 1157, 1116, 987, 852, 812, 753, 681, 638 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C23H30NO8 + [M+H] + : ; Found: S20

22 White foam (93% yield, 94% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 10/90, 0.80 ml/min, λ = 343 nm: tr (major) = 12.8 min, tr (minor) = 25.8 min.); [α]d 28 = (c 1.02, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 6.65 (dd, J = 8.8, 2.8 Hz, 1H), 6.46 (d, J = 8.8 Hz, 1H), 6.35 (d, J = 2.4 Hz, 1H), 4.12 (d, J = 2.0 Hz, 1H), (m, 12H), 3.42 (s, 3H), 2.91 (d, J = 15.6 Hz, 1H), 2.78 (s, 3H), (m, 2H), 2.37 (ABd, J = 16.0 Hz, 1H), 1.39 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.1, 171.3, 170.8, 169.1, 153.5, 146.9, 136.6, 113.1, 111.0, 109.5, 75.3, 57.7, 55.7, 52.8, 52.7, 52.5(2), 52.4(6), 51.6, 44.7, 41.5, 35.0, 33.4, 26.8; IR (neat): 2950, 1740, 1717, 1496, 1454, 1430, 1339, 1288, 1261, 1224, 1163, 1116, 1077, 1056, 1031, 986, 961, 929, 870, 845, 821, 779, 755, 701, 671, 642 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C23H30NO9 + [M+H] + : ; Found: White foam (99% yield, 97% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 254 nm: tr (major) = 14.6 min, tr (minor) = 21.2 min.); [α]d 28 = +9.6 (c 0.99, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 7.01 (dd, J = 8.4, 2.0 Hz, 1H), 6.66 (d, J = 2.0 Hz, 1H), 6.38 (d, J = 8.4 Hz, 1H), 4.21 (d, J = 1.6 Hz, 1H), 3.78 (s, 3H), 3.68(2)- 3.67(6) (m, 6H), 3.50 (s, 3H), 2.92 (d, J = 16.0 Hz, 1H), 2.79 (s, 3H), (m, 2H), 2.37 (ABd, J = 16.0 Hz, 1H), 1.37 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 171.9, 171.1, 170.5, 169.0, 151.0, 136.7, 128.3, 122.7(4), 122.6(7), 110.1, 74.9, 57.2, 52.9, 52.7, 52.5, 51.5, 44.5, 39.1, 34.7, 33.0, 26.8; IR (neat): 2954, 1728, 1600, 1485, 1455, 1433, 1235, 1210, 1168, 1114, 1048, 991, 856, 813, 769, 752, 637 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27ClNO8 + [M+H] + : ; Found: S21

23 White foam (99% yield, 97% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 274 nm: tr (major) = 15.0 min, tr (minor) = 20.7 min.); [α]d 28 = +1.5 (c 0.99, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 7.15 (dd, J = 8.4, 2.0 Hz, 1H), 6.79 (d, J = 2.0 Hz, 1H), 6.34 (d, J = 8.4 Hz, 1H), 4.21 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), 3.68(2)- 3.67(6) (m, 6H), 3.52 (s, 3H), 2.92 (d, J = 15.6 Hz, 1H), 2.78 (s, 3H), 2.53 (dd, J = 15.6, 2.0 Hz, 1H), 2.46 (ABd, J = 16.0 Hz, 1H), 2.36 (ABd, J = 16.0 Hz, 1H), 1.37 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 171.9, 171.0, 170.5, 169.1, 151.4, 137.1, 131.2, 125.5, 110.6, 109.7, 74.9, 57.2, 53.1, 52.9, 52.7, 52.6, 51.5, 44.5, 38.9, 34.7, 33.0, 26.8; IR (neat): 2955, 1730, 1490, 1480, 1455, 1433, 1234, 1211, 1165, 1115, 1048, 991, 855, 811, 750, 630 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27BrNO8 + [M+H] + : ; Found: White foam (98% yield, 96% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 254 nm: tr (major) = 16.2 min, tr (minor) = 25.2 min.); [α]d 28 = (c 0.99, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 6.77 (dt, J = 8.4, 2.0 Hz, 1H), (m, 2H), 4.18 (d, J = 1.6 Hz, 1H), 3.78 (s, 3H), (m, 6H), 3.47 (s, 3H), 2.91 (d, J = 15.6 Hz, 1H), 2.79 (s, 3H), 2.54 (dd, J = 16.0, 2.0 Hz, 1H), 2.46 (ABd, J = 16.0 Hz, 1H), 2.38 (ABd, J = 16.0 Hz, 1H), 1.38 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.0, 171.2, 170.6, 169.0, (J = Hz), 148.8, (J = 6.9 Hz), (J = 23.5 Hz), (J = 8.4 Hz), (J = 23.9 Hz), 75.2, 57.5, 52.9, 52.8, 52.6, 52.5, 51.5, 44.6, 40.5, 34.8, 33.2, 26.8; 19 F NMR (375 MHz, CDCl3): ; IR (neat): 2969, 1747, 1723, 1500, 1434, 1240, 1218, 1185, 1108, 1080, 877, 851, 819, 776, 755, 705, 645, 624 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27FNO8 + [M+H] + : S22

24 ; Found: White foam (99% yield, 93% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 254 nm: tr (major) = 14.5 min, tr (minor) = 17.6 min.); [α]d 28 = (c 1.01, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 6.60 (d, J = 7.6 Hz, 1H), 6.44 (d, J = 7.6 Hz, 1H), 6.31 (s, 1H), 4.17 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), (m, 6H), 3.41 (s, 3H), 2.91 (d, J = 15.6 Hz, 1H), 2.79 (s, 3H), (m, 2H), 2.35 (ABd, J = 16.0 Hz, 1H), 2.26 (s, 3H), 1.36 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.2, 171.4, 170.7, 169.3, 152.7, 138.3, 131.9, 122.2, 119.1, 110.3, 75.0, 57.4, 52.8, 52.7, 52.6, 52.5, 51.7, 44.2, 39.4, 34.9, 33.4, 26.8, 21.6; IR (neat): 2955, 1744, 1725, 1612, 1593, 1498, 1469, 1437, 1415, 1267, 1235, 1213, 1167, 1116, 1083, 1041, 1017, 986, 963, 930, 855, 801, 753, 691, 638 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C23H30NO8 + [M+H] + : ; Found: White foam (99% yield, 95% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 334 nm: tr (major) = 17.9 min, tr (minor) = 22.5 min.); [α]d 29 = (c 1.02, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 6.72 (dd, J = 7.6, 1.2 Hz, 1H), (m, 2H), 4.22 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), (m, 6H), 3.44 (s, 3H), 2.88 (d, J = 16.0 Hz, 1H), 2.78 (s, 3H), (m, 2H), 2.36 (ABd, J = 16.0 Hz, 1H), 1.34 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 171.9, 171.3, 170.5, 169.1, 153.6, 133.8, 123.7, 122.1, 120.6, 111.9, 74.8, 57.1, 52.9(3), 52.8(8), 52.7, 52.6, 51.6, 44.3, 38.3, 34.6, 33.0, 26.8; IR (neat): 2955, 1758, 1732, 1597, 1581, 1494, 1456, 1435, 1411, 1253, 1231, 1204, 1169, 1115, 1085, 1039, 1012, 990, 963, 930, 887, 851, 822, 802, 758, 648 S23

25 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27BrNO8 + [M+H] + : ; Found: White foam (97% yield, 93% ee, >99/1 dr); (Chiralcel IF, i-proh/co2 = 10/90, 1.30 ml/min, λ = 230 nm: tr (minor) = 10.1 min, tr (major) = 11.2 min.); [α]d 29 = (c 0.99, CHCl3); 1 H NMR (400 MHz, CDCl3): δ (m, 2H), 6.41 (d, J = 1.2 Hz, 1H), 4.23 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), 3.68(3)-3.67(6) (m, 6H), 3.44 (s, 3H), 2.89 (d, J = 16.0 Hz, 1H), 2.79 (s, 3H), (m, 2H), 2.36 (ABd, J = 16.0 Hz, 1H), 1.35 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 171.9, 171.3, 170.5, 169.1, 153.4, 134.1, 133.2, 123.2, 117.7, 109.0, 74.9, 57.1, 52.9(5), 52.8(9), 52.8, 52.6, 51.6, 44.2, 38.3, 34.6, 33.1, 26.7; IR (neat): 2955, 1732, 1599, 1495, 1434, 1231, 1169, 1114, 1039, 991, 930, 851, 826, 803 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27ClNO8 + [M+H] + : ; Found: White foam (96% yield, 94% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 2/98, 0.80 ml/min, λ = 280 nm: tr (minor) = 36.1 min, tr (major) = 41.6 min.); [α]d 30 = (c 1.00, CHCl3); 1 H NMR (400 MHz, CDCl3): δ (m, 1H), 6.27 (t, J = 8.6 Hz, 1H), 6.14 (d, J = 10.0 Hz, 1H), 4.24 (s, 1H), 3.78 (s, 3H), 3.68(2)-3.67(5) (m, 6H), 3.44 (s, 3H), 2.91 (d, J = 16.0 Hz, 1H), 2.78 (s, 3H), (m, 2H), 2.35 (ABd, J = 16.0 Hz, 1H), 1.35 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.0, 171.3, 170.5, 169.2, (J = Hz), (J = 12.6 Hz), 129.9, (J = 10.1 Hz), (J = 22.8 Hz), 96.6 (J = 27.0 Hz), 75.1, 57.1, 52.9, 52.8, 52.7, 52.6, 51.6, 44.0, 38.4, 34.9, 33.2, 26.7; 19 F NMR (375 MHz, CDCl3): ; IR (neat): 2955, 1753, 1728, 1617, 1497, 1434, 1257, 1160, 1108, 1047, 992, 845, 789, 753, 616 cm -1 ; HRMS-ESI (m/z): Exact mass S24

26 calcd. for C22H27FNO8 + [M+H] + : ; Found: White foam (98% yield, 93% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 254 nm: tr (minor) = 11.5 min, tr (major) = 14.5 min.); [α]d 29 = (c 1.01, CHCl3); 1 H NMR (400 MHz, CDCl3): δ (m, 1H), (m, 2H), 4.18 (d, J = 1.6 Hz, 1H), 3.81 (s, 3H), (m, 6H), 3.44 (s, 3H), 3.03 (s, 3H), (m, 4H), 1.43 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 171.9, 171.4, 170.7, 168.8, 149.2, 139.6, 129.6, 121.5, 121.1, 118.9, 75.9, 57.9, 52.9, 52.8, 52.6, 51.5, 44.9, 42.4, 34.4, 33.2, 26.9; IR (neat): 2958, 1732, 1597, 1434, 1257, 1200, 1122, 1055, 989, 858, 834, 783, 749, 643 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27ClNO8 + [M+H] + : ; Found: White foam (98% yield, 95% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 254 nm: tr (minor) = 11.3 min, tr (major) = 15.6 min.); [α]d 29 = (c 0.99, CHCl3); 1 H NMR (400 MHz, CDCl3): δ 7.23 (dd, J = 15.6, 1.2 Hz, 1H), (m, 2H), 4.19 (d, J = 1.6 Hz, 1H), 3.81 (s, 3H), (m, 6H), 3.44 (s, 3H), 3.04 (s, 3H), (m, 4H), 1.44 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ 171.8, 171.4, 170.7, 168.8, 150.8, 139.9, 132.7, 122.1, 121.8, 107.5, 76.0, 58.0, 53.0, 52.9, 52.8, 52.6, 51.5, 44.9, 43.1, 34.4, 33.2, 27.0; IR (neat): 2957, 1754, 1732, 1594, 1573, 1449, 1433, 1416, 1256, 1230, 1199, 1166, 1121, 1052, 1018, 989, 964, 931, 856, 811, 781, 750, 686, 642 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C22H27BrNO8 + [M+H] + : ; Found: S25

27 White foam (93% yield, 82% ee, >99% ee after recrystallization, >99/1 dr); (Chiralcel OD-H, i-proh/co2 = 10/90, 1.30 ml/min, λ = 214 nm: tr (major) = 7.5 min, tr (minor) = 8.1 min.); [α]d 28 = (c 0.98, CHCl3); 1 H NMR (400 MHz, CDCl3): δ (m, 1H), (m, 2H), 6.45 (d, J = 8.0 Hz, 1H), 4.41 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), (m, 6H), 3.40 (s, 3H), (m, 4H), (m, 1H), 2.93 (d, J = 15.6 Hz, 1H), 2.77 (s, 3H), (m, 2H), 2.42 (ABd, J = 15.6 Hz, 1H), (m, 1H), (m, 1H); 13 C NMR (100 MHz, CDCl3): δ 172.1, 171.4, 170.7, 169.3, 153.2, 131.5, 128.7, 123.0, 118.0, 108.9, 72.4, 69.0, 58.5, 57.2, 52.9, 52.8, 52.6, 52.5, 51.6, 46.9, 43.2, 38.5, 34.6, 26.8; IR (neat): 2952, 1731, 1604, 1490, 1458, 1433, 1227, 1195, 1160, 1111, 993, 855, 743 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C24H32NO9 + [M+H] + : ; Found: White foam (92% yield, 83% ee, >99% ee after recrystallization, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 5/95, 0.80 ml/min, λ = 254 nm: tr (major) = 20.4 min, tr (minor) = 29.1 min.); [α]d 30 = (c 1.00, CHCl3); 1 H NMR (400 MHz, CDCl3): δ (m, 1H), 6.72 (dd, J = 7.2, 0.8 Hz, 1H), (m, 1H), 6.44 (d, J = 8.0 Hz, 1H), (m, 3H), 4.22 (d, J = 2.0 Hz, 1H), 3.77 (s, 3H), (m, 6H), 3.41 (s, 3H), 2.93 (d, J = 15.6 Hz, 1H), 2.71 (s, 3H), (m, 2H), (m, 3H); 13 C NMR (100 MHz, CDCl3): δ 172.1, 171.4, 170.7, 169.2, 153.5, 133.9, 131.9, 128.6, 122.9, 118.6, 118.1, 109.0, 71.5, 57.2, 52.9, 52.8, 52.6, 52.5, 51.5, 48.6, 48.3, 38.4, 34.2, 27.2; IR (neat): 2952, 1732, 1605, 1490, 1455, 1252, 1190, 1115, 1079, 1048, 1008, 981, 953, 925, 852, 745, 625 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C24H30NO8 + [M+H] + : ; Found: S26

28 White foam (83% yield, 81% ee, >99/1 dr]; (Chiralcel AD-H, i-proh/hexanes = 15/85, 0.80 ml/min, λ = 254 nm: tr (major) = 12.6 min, tr (minor) = 14.8 min.); [α]d 27 = +2.5 (c 0.50, CHCl3, 97% ee); 1 H NMR (400 MHz, CDCl3): δ (m, 1H), (m, 2H), 6.46 (d, J = 8.0 Hz, 1H), 4.31 (d, J = 2.0 Hz, 1H), 3.79 (s, 3H), (m, 6H), 3.40 (s, 3H), (m, 1H), (m, 2H), 2.78 (s, 3H), (m, 2H), 2.43 (ABd, J = 15.6 Hz, 1H), (m, 1H), (m, 1H); 13 C NMR (100 MHz, CDCl3): δ 171.9, 171.2, 170.6, 169.0, 152.8, 130.5, 129.1, 122.8, 118.3, 109.0, 71.9, 57.1, 53.0, 52.8, 52.7, 52.6, 51.4, 47.1, 46.9, 42.1, 38.2, 34.2, 26.8; IR (neat): 2945, 2102, 1729, 1603, 1494, 1434, 1257, 1228, 1196, 1115, 989, 851, 771, 755, 459 cm -1 ; HRMS-ESI (m/z): Exact mass calcd. for C23H29N4O8 + [M+H] + : ; Found: With 10 mol% catalyst, [1a] = mol/l. White foam (99% yield, 90% ee, >99/1 dr); (Chiralcel IA-3, i-proh/hexanes = 10/90, 0.80 ml/min, λ = 254 nm: tr (minor) = 12.0 min, tr (major) = 13.5 min.); [α]d 29 = (c 1.00, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), (m, 1H), (m, 2H), 6.51 (d, J = 7.6 Hz, 1H), 4.58 (ABd, J = 16.4 Hz, 1H), 4.40 (d, J = 2.0 Hz, 1H), 4.01 (ABd, J = 16.0 Hz, 1H), 3.67(3) (s, 3H), 3.66(6) (s, 3H), 3.50 (s, 3H), 3.41 (s, 3H), 3.05 (d, J = 15.6 Hz, 1H), 2.63 (dd, J = 15.6, 2.0 Hz, 1H), 2.51 (ABd, J = 16.0 Hz, 1H), 2.33 (ABd, J = 15.6 Hz, 1H), 1.10 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 172.2, 171.3, 170.6, 169.2, 152.1, 138.5, 135.4, 128.4, 127.6, 127.1, 122.6, 118.9, 110.8, 71.9, 57.7, 56.4, 52.9, 52.8, 52.6, 52.5, 51.7, 44.4, 35.1, 32.1, 26.9; IR (neat): 2956, 1750, 1721, 1597, 1486, 1451, 1261, S27

29 1223, 1165, 1112, 1028, 949, 852, 745, 707, 646 cm -1 ; HRMS-ESI: Exact mass calcd for C28H32NO8 + [M+H] + : ; Found: Experimental procedure for the scale-up reaction A mixture of Cu(OTf)2 (1.1 g, 3.0 mmol) and indole 1u (9.3 g, 30.0 mmol) in CH2Cl2 (100 ml) was stirred at 0 o C under nitrogen, the solution of 2a (90.0 mmol) in CH2Cl2 (100 ml) was then added dropwise to the system. The reaction was monitored by TLC, until the complete consumption of 1u. The reaction mixture was filtered through a thin layer of silica gel and eluted with CH2Cl2. The solvent was removed by reduced pressure and the residue was purified by flash chromatography over silica gel (EA/petroleum ether, 1/5-1/2) to afford the adduct rac-3bu (13.8 g, 77% yield). A mixture of Cu(OTf)2 (0.03 mmol) and phenyl bisoxazoline (Wing-BOX, mmol) in DCM (6 ml) was stirred at 30 o C for 2 h under nitrogen. Then, the system was cooled to -78 o C, the indole 1b (3.0 mmol) was added to the catalyst solution and 1.5 ml DCM was added to wash the tube wall, the solution of 2a (9.0 mmol) in DCM (1.5 ml) was then added dropwise to the system. When the reaction was completed (monitored by TLC), the reaction mixture was filtered through a thin layer of silica gel and eluted with CH2Cl2. The solvent was removed by reduced pressure and the residue was purified by flash chromatography over silica gel (EA/petroleum ether, 1/5-1/4) to afford the product 3ba (1.27g, 98%yield, 96% ee). S28

30 6. Experimental procedure for transformation of rac-3bu and 3br A mixture of Pd(OAc)2 (0.06 mol, 13.5 mg), Et3N (0.18 mmol, 18.2 mg) and Et3SiH ( mmol, mg) in CH2Cl2 (1.0 ml) was stirred at room temperature for 15 minutes under nitrogen. The solution of rac-3bu (0.2 mmol, mg) in DCM (1.0 ml) was then added dropwise to the system. The reaction was monitored by TLC, until the complete consumption of rac-3bu. The reaction mixture was filtered through a thin layer of celite and eluted with CH2Cl2. The solvent was removed by reduced pressure and the residue was purified by flash chromatography over silica gel (EtOH/DCM, 1/20) to afford the deprotected product rac-4 (87.4 mg, 94% yield). White foam (94% yield, >99/1 dr); 1 H NMR (400 MHz, CDCl3) δ 6.99 (t, J = 7.4 Hz, 1H), (m, 2H), 6.37 (d, J = 8.0 Hz, 1H), 4.19 (s, 1H), 3.71 (s, 3H), (m, 6H), 3.33 (s, 3H), 2.84 (d, J = 15.6 Hz, 1H), 3.70 (s, 3H), (m, 2H), 2.32 (d, J = 15.6 Hz, 1H), (m, 2H); 13 C NMR (100 MHz, CDCl3): δ 171.8, 171.1, 170.4, 168.9, 152.7, 131.4, 128.5, 122.7, 117.9, 108.8, 72.1, 57.0, 52.6(9), 52.6(8), 52.6, 52.5, 52.5, 52.3(3), 52.3(2), 51.3, 38.1, 34.3, 26.7; IR (neat): 2953, 1733, 1603, 1490, 1455, 1433, 1254, 1234, 1172, 1115, 1044, 1022, 997, 854, 749 cm -1 ; HRMS-ESI: Exact mass calcd for C23H31N2O8 + [M+H] + : ; Found: A Schlenk tube was charged with mg (1 mmol) of rac-4 and 8 ml of MeOH, S29

31 the solution was stirred at room temperature under nitrogen. Then 2 ml of NaOMe (5 mol/l, dissolved in MeOH) was added slowly to the system. The reaction was then allowed to stir at 65 o C for two days. The mixture was filtered through a thin layer of silica gel, eluting with acetone, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography over silica gel (ethyl acetate/petroleum ether, 1/1) to afford product rac- 5 (202.3 mg, 47% yield). A mixture of rac-5 (129.0 mg, 0.3 mmol), LiCl (76.3 mg, 1.8 mmol) and H2O (32.4 mg, 1.8 mmol) in DMSO (5 ml) was stirred at 130 o C under nitrogen. The reaction was monitored by TLC, until the complete consumption of rac-5. The reaction mixture was then poured into water and extracted with ethyl acetate (20 ml 3). The combined organic layers were dried over anhydrous Na2SO4, filtered and concentrated. The residue was purified by column chromatography over silica gel (ethyl acetate/petroleum ether 3/1) to afford rac-6 (67.8 mg, 60% yield, 2/1 isolated d.r.). A mixture of Cu(OTf)2 (0.1 mmol) and phenyl bisoxazoline (Wing-BOX, 0.12 mmol) in DCM (60 ml) was stirred at 30 o C for 2 h under nitrogen. Then, the system was cooled to -78 o C, the solution of 1r (1 mmol) in DCM (5 ml) and the solution of 2a (3 mmol) in DCM (5 ml) was added dropwise to the system at the same time. When the reaction was completed (monitored by TLC), the reaction mixture was filtered through a thin layer of silica gel and eluted with CH2Cl2. The solvent was removed by reduced pressure and the residue was purified by flash chromatography over silica gel (EA/petroleum ether, 1/5) to afford the product 3br with 81% ee, most of the minor enantiomer was easy to precipitate through recrystallization and affording the desired S30

32 product with 97% ee in the residue. A mixture of 3br (0.51 mmol) and 10% wt Pd/C (0.051 mmol) in MeOH (6 ml) was stirred at 30 o C for 2 h under hydrogen atmosphere. When the reaction was completed (monitored by TLC), the reaction mixture was filtered through kiesieguhr and eluted with EtOH. The solvent was removed by reduced pressure. A Schlenk tube was charged with above crude product and 4 ml of dry MeOH, the solution was stirred at room temperature under nitrogen. Then 5.1 ml of NaOMe (5 mol/l, dissolved in MeOH) was added slowly to the system. The reaction was then allowed to stir at 65 o C for 12 h. The mixture was filtered through a thin layer of silica gel, eluting with acetone, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography over silica gel (ethyl acetate/petroleum ether, 1.5/1-2/1) to afford product 5 (98.8 mg, 45% yield). A mixture of 5 (0.23 mmol), LiCl (1.38 mmol) and H2O (1.38 mmol) in DMSO (4 ml) was stirred at 130 o C under nitrogen. The reaction was monitored by TLC, until the complete consumption of 5. The reaction mixture was then poured into water and extracted with ethyl acetate (20 ml 3). The combined organic layers were dried over anhydrous Na2SO4, filtered and concentrated. The residue was purified by column chromatography over silica gel (ethyl acetate/petroleum ether 1.5/1-3/1) to afford 6 (53.1 mg, 62% yield, 1.3/1 isolated d.r.). White foam (45% yield, 97% ee, >99/1 dr); (Chiralcel AD-H, i-proh/hexanes = 40/60, 0.80 ml/min, λ = 254 nm: tr (major) = 10.3 min, tr (minor) = 12.3 min.); [α]d 18 = (c 0.47, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.09 (t, J = 7.8 Hz, 1H), 6.94 (d, J = 7.2 Hz, 1H), 6.66 (d, J = 7.4 Hz, 1H), (m, 2H), 4.35 (s, 1H), (m, 6H), (m, 5H), (m, 1H), 2.83 (s, 3H), (m, 2H), (m, 3H); 13 C NMR (100 MHz, CDCl3): δ 176.6, 172.5, 172.4, 167.3, 150.3, 136.2, 128.5, 121.9, 117.5, 106.8, 71.1, 55.4, 53.3, 52.7, 52.4, 52.3, 46.3, 42.8, 38.3, 35.4, 34.1, S31

33 31.1; IR (neat): 2953, 2919, 2850, 1730, 1649, 1605, 1504, 1487, 1453, 1432, 1361, 1250, 1230, 1152, 1128, 1091, 1038, 1003, 970, 842, 803, 753, 734 cm -1 ; HRMS-ESI: Exact mass calcd for C22H27N2O7 + [M+H] + : ; Found: White foam (62% yield, 97% ee of both isomers, 1.3/1 isolated dr); 6-Major: (Chiralcel AD-H, i-proh/hexanes = 30/70, 0.80 ml/min, λ = 254 nm: tr (major) = 10.3 min, tr (minor) = 15.9 min.); [α]d 23 = (c 0.48, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 1H), 6.92 (d, J = 7.2 Hz, 1H), 6.61 (t, J = 7.2 Hz, 2H), 6.35 (d, J = 7.6 Hz, 1H), 3.72 (s, 3H), (m, 4H), (m, 1H), (m, 1H), 2.99 (dd, J = 15.2, 3.6 Hz, 1H), 2.64 (s, 3H), (m, 1H), 2.40 (d, J = 14.8 Hz, 1H), (m, 1H), (m, 3H); 13 C NMR (100 MHz, CDCl3): δ 176.1, 175.8, 172.1, 150.5, 136.1, 128.6, 122.1, 118.0, 107.2, 71.3, 52.8, 52.5, 52.3, 45.5, 42.8, 42.1, 39.1, 35.1, 34.2, 27.9; IR (neat): 3370, 2945, 2925, 1734, 1664, 1602, 1489, 1456, 1440, 1265, 1245, 1191, 1154, 1138, 1117, 1083, 1025, 989, 764, 748, 729 cm -1 ; HRMS-ESI: Exact mass calcd for C20H25N2O5 + [M+H] + : ; Found: Minor: (Chiralcel OD-H, i-proh/hexanes = 40/60, 0.80 ml/min, λ = 254 nm: tr (minor) = 10.8 min, tr (major) = 24.0 min.); [α]d 23 = (c 0.48, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 1H), 7.02 (d, J = 7.2 Hz, 1H), (m, 2H), 6.60 (d, J = 8.0 Hz, 1H), 4.01 (t, J = 14.0 Hz, 1H), 3.76 (s, 3H), 3.68 (s, 3H), 3.36 (d, J = 2.8 Hz, 1H), (m, 1H), (m, 1H), (m, 6H), 2.39 (t, J = 13.6 Hz, 1H), (m, 1H), 1.51 (d, J = 14.8 Hz, 1H); 13 C NMR (100 MHz, CDCl3): δ 173.9, 173.6, 172.2, 151.0, 137.6, 128.1, 120.8, 119.2, 109.1, 75.4, 55.3, 52.7, 52.0, 45.1, 40.0, 38.1, 37.6, 35.2, 34.4, 28.9; IR (neat): 2922, 2852, 1742, 1725, 1647, 1605, 1481, 1458, 1435, 1362, 1252, 1217, 1135, 1103, 1023, 982, 956, 800, 759, 733, 617, 535, 462 cm -1 ; HRMS-ESI: Exact mass calcd for C20H25N2O5 + [M+H] + : ; Found: S32

34 7. Copies of NMR Spectra Racemic reaction S33

35 S34

36 S35

37 S36

38 S37

39 S38

40 S39

41 S40

42 S41

43 S42

44 S43

45 S44

46 S45

47 S46

48 Enantioselective reaction S47

49 S48

50 S49

51 S50

52 S51

53 S52

54 S53

55 S54

56 S55

57 S56

58 S57

59 S58

60 S59

61 S60

62 S61

63 S62

64 S63

65 S64

66 S65

67 S66

68 S67

69 S68

70 S69

71 S70

72 S71

73 S72

74 S73

75 S74

76 8. Copies of HPLC Data S75

77 S76

78 S77

79 S78

80 S79

81 S80

82 S81

83 S82

84 S83

85 S84

86 S85

87 S86

88 S87

89 S88

90 S89

91 S90

92 After recrystallization S91

93 S92

94 After recrystallization S93

95 S94

96 After recrystallization S95

97 S96

98 S97

99 S98

100 S99

101 9. X-ray Data Table S10. Crystal data and structure refinement for CD16074 (CCDC ). Identification code cd16074 Empirical formula Formula weight Temperature Wavelength Crystal system S100 C20 H24 N2 O5 293(2) K Å Monoclinic Space group P 21/c Unit cell dimensions a = (4) Å = 90. b = (13) Å = (4). c = (3) Å = 90. Volume (6) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 792 Crystal size x x mm 3 Theta range for data collection to Index ranges Reflections collected <=h<=21, -5<=k<=8, -18<=l<=19 Independent reflections 3481 [R(int) = ] Completeness to theta = % Absorption correction Mutil-scan Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3481 / 0 / 251 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient Largest diff. peak and hole and e.å -3 n/a

102 Table S11 Crystal data and structure refinement for cd15163 (CCDC ). Identification code Empirical formula cd15163 Formula weight Temperature Wavelength Crystal system C22 H26 Br N O8 293(2) K Å Orthorhombic Space group P Unit cell dimensions a = (2) Å = 90. b = (19) Å = 90. c = (7) Å = 90. Volume (14) Å 3 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 2112 Crystal size x x mm 3 Theta range for data collection to Index ranges Reflections collected <=h<=13, -13<=k<=13, -45<=l<=45 Independent reflections 8550 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 8550 / 13 / 599 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.027(7) Extinction coefficient Largest diff. peak and hole and e.å -3 n/a S101

103 Table S12 Crystal data and structure refinement for cd16028 (CCDC ). Identification code Empirical formula cd16028 Formula weight Temperature Wavelength Crystal system C21 H22 Br2 Cu N2 O2 293(2) K Å Orthorhombic Space group P Unit cell dimensions a = (10) Å = 90. b = (13) Å = 90. c = (2) Å = 90. Volume (4) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1108 Crystal size x x mm 3 Theta range for data collection to Index ranges Reflections collected <=h<=10, -14<=k<=14, -25<=l<=24 Independent reflections 4294 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4294 / 0 / 255 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.009(8) Extinction coefficient Largest diff. peak and hole and e.å -3 n/a S102

104 Table S13 Crystal data and structure refinement for cd16001 (CCDC ). Identification code Empirical formula cd16001 Formula weight Temperature Wavelength Crystal system C29 H34 Br2 Cu N2 O2 293(2) K Å Tetragonal Space group P Unit cell dimensions a = (11) Å = 90. b = (11) Å = 90. c = (3) Å = 90. Volume (6) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1348 Crystal size x x mm 3 Theta range for data collection to Index ranges Reflections collected <=h<=14, -13<=k<=14, -19<=l<=23 Independent reflections 2575 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2575 / 6 / 173 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.046(16) Extinction coefficient Largest diff. peak and hole and e.å -3 n/a S103

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