Supporting Information For Elumalai Gopi and Irishi N. N ... · Elumalai Gopi and Irishi N. N....
75
1 Supporting Information For Synthesis of α-Tribromomethylamines via Mg-Mediated Addition of Bromoform to Imines Elumalai Gopi and Irishi N. N. Namboothiri* Department of Chemistry and Indian Institute of Technology, Bombay, Mumbai 400 076 [email protected] Table of Contents Entry Page 01 Figure S1. 1 H NMR Spectrum of 6a 04 02 Figure S2. 13 C NMR Spectrum of 6a 05 03 Figure S3. 1 H NMR Spectrum of 6b 06 04 Figure S4. 13 C NMR Spectrum of 6b 07 05 Figure S5. 1 H NMR Spectrum of 6c 08 06 Figure S6. 13 C NMR Spectrum of 6c 09 07 Figure S7. 1 H NMR Spectrum of 6d 10 08 Figure S8. 13 C NMR Spectrum of 6d 11 09 Figure S9. 1 H NMR Spectrum of 6e 12 10 Figure S10. 13 C NMR Spectrum of 6e 13 11 Figure S11. 13 C-APT NMR Spectrum of 6e 14 12 Figure S12. 19 F NMR Spectrum of 6e 15 13 Figure S13. 1 H NMR Spectrum of 6f 16 14 Figure S14. 13 C NMR Spectrum of 6f 17 15 Figure S15. 1 H NMR Spectrum of 6g 18 16 Figure S16. 13 C NMR Spectrum of 6g 19 17 Figure S17. 1 H NMR Spectrum of 6h 20 18 Figure S18. 13 C NMR Spectrum of 6h 21 19 Figure S19. 1 H NMR Spectrum of 8a 22 20 Figure S20. 13 C NMR Spectrum of 8a 23 21 Figure S21. 13 C-APT NMR Spectrum of 8a 24 22 Figure S22. 1 H NMR Spectrum of 8b 25 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2014
Transcript of Supporting Information For Elumalai Gopi and Irishi N. N ... · Elumalai Gopi and Irishi N. N....
1
Supporting Information For
Synthesis of α-Tribromomethylamines via Mg-Mediated Addition of Bromoform to Imines
Elumalai Gopi and Irishi N. N. Namboothiri* Department of Chemistry and Indian Institute of Technology, Bombay, Mumbai 400 076
[email protected] Table of Contents
Entry Page 01 Figure S1. 1H NMR Spectrum of 6a 04 02 Figure S2. 13C NMR Spectrum of 6a 05 03 Figure S3. 1H NMR Spectrum of 6b 06 04 Figure S4. 13C NMR Spectrum of 6b 07 05 Figure S5. 1H NMR Spectrum of 6c 08 06 Figure S6. 13C NMR Spectrum of 6c 09 07 Figure S7. 1H NMR Spectrum of 6d 10 08 Figure S8. 13C NMR Spectrum of 6d 11 09 Figure S9. 1H NMR Spectrum of 6e 12 10 Figure S10. 13C NMR Spectrum of 6e 13 11 Figure S11. 13C-APT NMR Spectrum of 6e 14 12 Figure S12. 19F NMR Spectrum of 6e 15 13 Figure S13. 1H NMR Spectrum of 6f 16 14 Figure S14. 13C NMR Spectrum of 6f 17 15 Figure S15. 1H NMR Spectrum of 6g 18 16 Figure S16. 13C NMR Spectrum of 6g 19 17 Figure S17. 1H NMR Spectrum of 6h 20 18 Figure S18. 13C NMR Spectrum of 6h 21 19 Figure S19. 1H NMR Spectrum of 8a 22 20 Figure S20. 13C NMR Spectrum of 8a 23 21 Figure S21. 13C-APT NMR Spectrum of 8a 24 22 Figure S22. 1H NMR Spectrum of 8b 25
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2014
2
23 Figure S23. 13C NMR Spectrum of 8b 26 24 Figure S24. 1H NMR Spectrum of 8c 27 25 Figure S25. 13C NMR Spectrum of 8c 28 26 Figure S26. 1H NMR Spectrum of 10a 29 27 Figure S27. 13C NMR Spectrum of 10a 30 28 Figure S28. 1H NMR Spectrum of 10b 31 29 Figure S29. 13C NMR Spectrum of 10b 32 30 Figure S30. 13C-APT NMR Spectrum of 10b 33 31 Figure S31. 1H NMR Spectrum of 10c 34 32 Figure S32. 13C NMR Spectrum of 10c 35 33 Figure S33. 13C-APT NMR Spectrum of 10c 36 34 Figure S34. 1H NMR Spectrum of 10d 37 35 Figure S35. 13C NMR Spectrum of 10d 38 36 Figure S36. 13C-APT NMR Spectrum of 10d 39 37 Figure S37. 1H NMR Spectrum of 10e 40 38 Figure S38. 13C NMR Spectrum of 10e 41 39 Figure S39. 13C-APT NMR Spectrum of 10e 42 40 Figure S40. 1H NMR Spectrum of 10f 43 41 Figure S41. 13C NMR Spectrum of 10f 44 42 Figure S42. 13C-APT NMR Spectrum of 10f 45 43 Figure S43. 1H NMR Spectrum of 12a 46 44 Figure S44. 13C NMR Spectrum of 12a 47 45 Figure S45. 1H NMR Spectrum of 12b 48 46 Figure S46. 13C NMR Spectrum of 12b 49 47 Figure S47. 1H NMR Spectrum of 12c 50 48 Figure S48. 13C NMR Spectrum of 12c 51 49 Figure S49. 1H NMR Spectrum of 12d 52 50 Figure S50. 13C NMR Spectrum of 12d 53 51 Figure S51. 1H NMR Spectrum of 12e 54 52 Figure S52. 13C NMR Spectrum of 12e 55 53 Figure S53. 13C-APT NMR Spectrum of 12e 56 54 Figure S54. 19F NMR Spectrum of 12e 57 55 Figure S55. 1H NMR Spectrum of 12f 58
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56 Figure S56. 13C NMR Spectrum of 12f 59 57 Figure S57. 1H NMR Spectrum of 13a 60 58 Figure S58. 13C NMR Spectrum of 13a 61 59 Figure S59. 1H NMR Spectrum of 13b 62 60 Figure S60. 13C NMR Spectrum of 13b 63 61 Figure S61. 1H NMR Spectrum of 13c 64 62 Figure S62. 13C NMR Spectrum of 13c 65 63 Figure S63. 1H NMR Spectrum of 13d 66 64 Figure S64. 13C NMR Spectrum of 13d 67 65 Figure S65. 1H NMR Spectrum of 13e 68 66 Figure S66. 13C NMR Spectrum of 13e 69 67 Figure S67. 19F NMR Spectrum of 13e 70 68 Figure S68. 1H NMR Spectrum of 18 71 69 Figure S69. 13C NMR Spectrum of 18 72 70 Figure S70. 13C-APT NMR Spectrum of 18 73 71 Figure S71. 1H-1H COSY NMR Spectrum of 18 74 72 Figure S72. 1H-1H COSY NMR Spectrum of 18 75
4
Fig S1. 1H NMR Spectrum of 6a
10 9 8 7 6 5 4 3 2 1 ppm
0.17
0.45
1.20
1.27
0.41
0.40
0.77
0.85
0.81
0.25
0.80
NAME INN-gopi-IM-Br3-4-1HEXPNO 27PROCNO 1Date_ 20110521Time 20.00INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 31DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 144DW 60.800 usecDE 6.50 usecTE 295.1 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300088 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
5
Fig S2. 13C NMR Spectrum of 6a 200 180 160 140 120 100 80 60 40 20 0 ppm
21.33
21.61
48.13
73.11
76.88
77.20
77.52
127.37
128.64
129.39
129.64
131.56
136.73
139.15
143.58
NAME INN-gopi-IM-Br3-4-13CEXPNO 28PROCNO 1Date_ 20110521Time 20.09INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 164DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 295.8 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127526 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
6
Fig S3. 1H NMR Spectrum of 6b
10 9 8 7 6 5 4 3 2 1 ppm
0.12
0.32
1.52
1.51
0.51
0.49
1.00
1.00
1.16
1.03
NAME INN-GOPI-1M-Br3-2-1HEXPNO 61PROCNO 1Date_ 20110518Time 23.50INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 73DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 32DW 60.800 usecDE 6.50 usecTE 295.7 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300085 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
HNTs
MeO
6b
7
Fig S4. 13C NMR Spectrum of 6b 200 180 160 140 120 100 80 60 40 20 0 ppm
21.60
48.90
55.42
72.90
76.88
77.20
77.52
113.29
126.48
127.37
129.42
131.04
136.76
143.56
160.16
NAME INN-GOPI-1M-Br3-2-13CEXPNO 62PROCNO 1Date_ 20110518Time 23.52INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 129DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 295.9 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127533 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
CBr3
HNTs
MeO
6b
8
Fig S5. 1H NMR Spectrum of 6c
10 9 8 7 6 5 4 3 2 1 ppm
0.06
0.22
1.88
1.90
1.91
0.62
1.25
1.24
1.25
0.11
1.26
NAME INN-gopi-IM-Br3-6-1HEXPNO 13PROCNO 1Date_ 20110529Time 14.58INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 46DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 71.8DW 60.800 usecDE 6.50 usecTE 300.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300032 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
HNTs
MeOOMe
6c
9
Fig S6. 13C NMR Spectrum of 6c 200 180 160 140 120 100 80 60 40 20 0 ppm
21.54
48.68
55.97
55.99
73.23
76.88
77.20
77.52
110.08
112.32
123.09
126.67
127.37
129.29
136.60
143.62
148.22
149.57
NAME INN-gopi-IM-Br3-6-13CEXPNO 14PROCNO 1Date_ 20110529Time 15.03INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 86DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 32DW 20.800 usecDE 6.50 usecTE 300.0 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127564 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
10
Fig S7. 1H NMR Spectrum of 6d
10 9 8 7 6 5 4 3 2 1 ppm
3.00
5.69
0.95
0.89
1.82
2.00
1.99
0.29
1.97
Current Data ParametersNAME INN-GOPI-IM-BR3-9-1HEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20130516Time 9.07INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 15DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 32DW 60.800 usecDE 6.50 usecTE 294.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
HNTs
NMe
Me6d
11
Fig S8. 13C NMR Spectrum of 6d 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
21.59
40.44
50.64
73.23
76.88
77.20
77.51
111.29
121.53
127.39
129.31
130.58
136.82
143.11
150.56
Current Data ParametersNAME INN-gopi-IM-Br3-9-13CEXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20130516Time 9.10INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 200DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 295.1 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127575 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
12
Fig S9. 1H NMR Spectrum of 6e
10 9 8 7 6 5 4 3 2 1 ppm
0.23
0.67
1.55
0.54
0.51
1.02
1.02
0.30
1.03
1.00
NAME INN-Gopi-IM-Br3-5-1HEXPNO 69PROCNO 1Date_ 20110528Time 22.25INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 144DW 60.800 usecDE 6.50 usecTE 300.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300081 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
HNTs
F
6e
13
Fig S10. 13C NMR Spectrum of 6e 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
21.61
47.40
72.60
76.94
77.20
77.45
114.86
115.03
127.32
129.51
130.34
131.65
131.71
136.54
143.94
162.03
164.02Current Data Parameters
NAME inn-gopi-im-br3-5a-13cEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20131020Time 10.14INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 269DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010048 secRG 197.27DW 16.800 usecDE 6.50 usecTE 294.6 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 8.90 usecPLW1 103.00000000 W
======== CHANNEL f2 ========SFO2 500.1320005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 13.00000000 WPLW12 0.34327999 WPLW13 0.21969999 W
F2 - Processing parametersSI 32768SF 125.7577697 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
14
Fig S11. 13C-APT NMR Spectrum of 6e 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
21.60
47.33
72.59
76.94
77.19
77.45
114.88
115.05
127.33
129.51
130.38
131.64
131.71
136.61
143.94
162.07
164.05Current Data Parameters
NAME DesktopEXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20131018Time 9.07INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG jmodTD 65536SOLVENT CDCl3NS 249DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010048 secRG 197.27DW 16.800 usecDE 6.50 usecTE 296.6 KCNST2 145.0000000CNST11 1.0000000D1 1.00000000 secD20 0.00689655 secTD0 1
======== CHANNEL f1 ========SFO1 125.7703643 MHzNUC1 13CP1 8.90 usecP2 17.80 usecPLW1 103.00000000 W
======== CHANNEL f2 ========SFO2 500.1320005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 13.00000000 WPLW12 0.34327999 W
F2 - Processing parametersSI 32768SF 125.7577688 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
15
Fig S12. 19F NMR Spectrum of 6e -200-180-160-140-120-100-80-60-40-200 ppm
-111.91
-111.90
-111.89
-111.88
-111.87
-111.87
-111.86
Current Data ParametersNAME INN-GOPI-IM-BR3-PF-19FEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20131201Time 8.17INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgflqnTD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767668 secRG 119.07DW 4.400 usecDE 6.50 usecTE 294.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5453180 MHzNUC1 19FP1 13.50 usecPLW1 40.00000000 W
F2 - Processing parametersSI 65536SF 470.5923770 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
-111.9 ppm
-111.913
-111.902
-111.895
-111.884
-111.874
-111.867
-111.856
16
Fig S13. 1H NMR Spectrum of 6f
10 9 8 7 6 5 4 3 2 1 ppm
0.07
1.46
0.51
0.52
1.01
0.52
1.04
1.10
1.00
NAME INN-Gopi-IM-Br3-1-1HEXPNO 3PROCNO 1Date_ 20130111Time 2.03INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 181DW 60.800 usecDE 6.50 usecTE 293.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
HNTs
O2N
6f
17
Fig S14. 13C NMR Spectrum of 6f 200 180 160 140 120 100 80 60 40 20 0 ppm
21.21
29.32
29.52
29.71
29.90
30.09
30.15
30.29
30.48
46.54
73.37
73.44
123.21
127.95
130.03
132.45
138.38
142.73
144.25
148.60
206.48
NAME INN-gopi-IM-Br3-1-13CEXPNO 24PROCNO 1Date_ 20110414Time 18.21INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT AcetoneNS 136DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 296.2 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6126773 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
CBr3
HNTs
O2N
6f
18
Fig S15. 1H NMR Spectrum of 6g
10 9 8 7 6 5 4 3 2 1 ppm
0.08
0.29
1.51
0.50
0.51
0.50
0.50
0.98
0.65
1.00
NAME INN-gopi-IM-Br3-7-1HEXPNO 15PROCNO 1Date_ 20110529Time 15.10INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 38DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 128DW 60.800 usecDE 6.50 usecTE 300.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300075 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
HNTs
O6g
19
Fig S16. 13C NMR Spectrum of 6g 200 180 160 140 120 100 80 60 40 20 0 ppm
21.68
45.84
67.80
76.88
77.20
77.52
110.71
112.02
127.21
129.61
136.75
142.83
143.83
147.34
NAME INN-gopi-IM-Br3-7-13CEXPNO 16PROCNO 1Date_ 20110529Time 15.15INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 83DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 32DW 20.800 usecDE 6.50 usecTE 300.0 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127532 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
CBr3
HNTs
O6g
20
Fig S17. 1H NMR Spectrum of 6h
10 9 8 7 6 5 4 3 2 1 ppm
0.19
1.20
0.42
0.40
0.39
0.40
0.77
0.42
0.24
0.79
NAME INN-gopi-IM-thio-1HEXPNO 30PROCNO 1Date_ 20110703Time 16.44INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 31DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 32DW 60.800 usecDE 6.50 usecTE 295.6 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
HNTs
S
6h
21
Fig S18. 13C NMR Spectrum of 6h 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
21.68
47.67
70.04
76.88
77.20
77.52
126.06
127.14
127.26
129.52
130.33
136.82
137.20
143.76Current Data Parameters
NAME INN-GOPI-IM-BR3-THIO1-1HEXPNO 5PROCNO 1
F2 - Acquisition ParametersDate_ 20131128Time 3.03INSTRUM spectPROBHD 5 mm SEI 1H/D-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 300DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 296.6 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 13.00 usecPL1 -3.00 dBPL1W 71.16858673 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 18.48 dBPL13 19.00 dBPL2W 16.73965454 WPL12W 0.11905469 WPL13W 0.10562007 WSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127541 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
22
Fig S19. 1H NMR Spectrum of 8a
10 9 8 7 6 5 4 3 2 1 ppm
0.95
2.90
1.00
0.97
1.01
1.01
3.99
3.39
1.93
Current Data ParametersNAME INN-gopi-IM-Br3-Ph-1HEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20130518Time 8.42INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 8DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 128DW 60.800 usecDE 6.50 usecTE 293.4 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
23
Fig S20. 13C NMR Spectrum of 8a 200 180 160 140 120 100 80 60 40 20 0 ppm
21.51
48.45
72.39
76.88
77.20
77.52
122.13
126.87
127.56
128.63
128.68
129.79
135.42
137.22
144.07
NAME INN-gopi-IM-Br3-Ph-13CEXPNO 22PROCNO 1Date_ 20110703Time 15.44INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 92DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 296.4 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127593 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
24
Fig S21. 13C-APT NMR Spectrum of 8a 200 180 160 140 120 100 80 60 40 20 0 ppm
21.56
48.34
72.33
76.94
77.20
77.45
122.31
126.92
127.60
128.70
128.77
129.82
135.46
137.31
137.38
144.13 Current Data Parameters
NAME INN-GOPI-IM-BR3-PH-APTEXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20131018Time 8.56INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG jmodTD 65536SOLVENT CDCl3NS 193DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010048 secRG 197.27DW 16.800 usecDE 6.50 usecTE 296.6 KCNST2 145.0000000CNST11 1.0000000D1 1.00000000 secD20 0.00689655 secTD0 1
======== CHANNEL f1 ========SFO1 125.7703643 MHzNUC1 13CP1 8.90 usecP2 17.80 usecPLW1 103.00000000 W
======== CHANNEL f2 ========SFO2 500.1320005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 13.00000000 WPLW12 0.34327999 W
F2 - Processing parametersSI 32768SF 125.7577702 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
25
Fig S22. 1H NMR Spectrum of 8b
10 9 8 7 6 5 4 3 2 1 ppm
0.08
0.09
0.25
1.40
1.45
0.48
0.46
0.48
0.48
0.96
1.40
0.67
1.00
NAME INN-GOPI-1H-C-OME-1HEXPNO 36PROCNO 2Date_ 20110701Time 22.34INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 35DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 90.5DW 60.800 usecDE 6.50 usecTE 295.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300104 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
26
Fig S23. 13C NMR Spectrum of 8b 200 180 160 140 120 100 80 60 40 20 0 ppm
21.52
49.05
55.62
72.93
76.88
77.20
77.52
111.03
120.62
122.47
124.36
127.45
127.56
129.67
129.84
132.55
137.38
143.83
157.10
NAME INN-gopi-IM-C-OMe-13CEXPNO 29PROCNO 1Date_ 20110703Time 16.38INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 119DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 296.4 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127557 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
27
Fig S24. 1H NMR Spectrum of 8c
10 9 8 7 6 5 4 3 2 1 ppm
1.55
1.50
0.51
0.50
0.50
1.04
1.06
1.00
1.03
1.00
Current Data ParametersNAME INN-GOPI-1M-Br3-17-1HEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20130910Time 10.44INSTRUM spectPROBHD 5 mm SEI 1H/D-PULPROG zg30TD 48074SOLVENT CDCl3NS 22DS 0SWH 9615.385 HzFIDRES 0.200012 HzAQ 2.4998479 secRG 32DW 52.000 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 6.75 usecPL1 -3.00 dBPL1W 16.73965454 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300103 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
HN
CBr3
Ts
8c
28
Fig S25. 13C NMR Spectrum of 8c 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
15.06
21.61
46.13
76.88
77.02
77.20
77.52
127.47
127.53
128.17
129.09
129.70
131.41
135.98
136.19
137.27
143.91Current Data Parameters
NAME INN-GOPI-IM-BR3-17-13CEXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20130912Time 13.49INSTRUM spectPROBHD 5 mm SEI 1H/D-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 97DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 295.2 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 13.00 usecPL1 -3.00 dBPL1W 71.16858673 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -3.00 dBPL12 18.48 dBPL13 19.00 dBPL2W 16.73965454 WPL12W 0.11905469 WPL13W 0.10562007 WSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127584 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
HN
CBr3
Ts
8c
29
Fig S26. 1H NMR Spectrum of 10a
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm
1.16
1.50
0.51
0.49
0.97
1.06
1.12
1.03
1.00
Current Data ParametersNAME INN-GOPI-BR3-IM-14-1HEXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20130507Time 22.23INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 10DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 32DW 60.800 usecDE 6.50 usecTE 294.3 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
HN
CBr3
Ts
10a
30
Fig S27. 13C NMR Spectrum of 10a 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
20.79
39.00
39.17
39.33
39.50
39.67
39.83
40.00
50.04
72.89
126.38
127.10
128.10
128.76
129.94
134.41
137.60
142.13
Current Data ParametersNAME inn-gopi-im-br3-14-13cEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20131023Time 7.05INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT DMSONS 235DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010048 secRG 197.27DW 16.800 usecDE 6.50 usecTE 295.5 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 8.90 usecPLW1 103.00000000 W
======== CHANNEL f2 ========SFO2 500.1320005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 13.00000000 WPLW12 0.34327999 WPLW13 0.21969999 W
F2 - Processing parametersSI 32768SF 125.7578545 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
HN
CBr3
Ts
10a
31
Fig S28. 1H NMR Spectrum of 10b
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm
1.50
1.60
1.56
0.50
0.48
0.51
1.52
0.54
0.05
1.00
Current Data ParametersNAME inn-gopi-br3-im-16-1hEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20130502Time 21.42INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 6DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 32DW 60.800 usecDE 6.50 usecTE 294.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
32
Fig S29. 13C NMR Spectrum of 10b 2030405060708090100110120130140150160170180190 ppm
19.60
19.74
21.54
48.25
73.28
76.88
77.20
77.52
127.17
127.34
129.11
130.97
131.65
135.92
136.60
137.47
143.28Current Data Parameters
NAME inn-gopi-br3-im-16-13CEXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20130502Time 21.48INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 31DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.1 KD1 1.00000000 secd11 0.03000000 secDELTA 0.89999998 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 WPLW13 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127603 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
33
Fig S30. 13C-APT NMR Spectrum of 10b
2030405060708090100110120130140150160170180190 ppm
19.60
19.73
21.54
48.26
73.29
76.88
77.20
77.52
127.17
127.34
129.11
130.98
131.65
135.91
136.61
137.46
143.26Current Data Parameters
NAME INN-GOPI-BR3-IM-16-APTEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20130505Time 1.15INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG jmodTD 65536SOLVENT CDCl3NS 49DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.5 KCNST2 145.0000000CNST11 1.0000000D1 1.00000000 secd20 0.00689655 secDELTA 0.00001114 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecp2 17.50 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127605 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
34
Fig S31. 1H NMR Spectrum of 10c
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm
1.00
0.37
0.36
0.34
0.36
0.67
1.61
0.31
0.74
Current Data ParametersNAME INN-GOPI-BR3-IM-15-1HEXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20130502Time 22.51INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 11DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 32DW 60.800 usecDE 6.50 usecTE 293.7 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
35
Fig S32. 13C NMR Spectrum of 10c 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
21.65
40.63
50.66
72.77
76.88
77.20
77.52
126.79
127.09
128.80
129.52
129.72
135.72
138.53
143.01Current Data Parameters
NAME INN-GOPI-BR3-IM-15-13cEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20130505Time 1.01INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 78DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.6 KD1 1.00000000 secd11 0.03000000 secDELTA 0.89999998 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 WPLW13 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127559 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
36
Fig S33. 13C-APT NMR Spectrum of 10c2030405060708090100110120130140150160170180190 ppm
21.65
40.67
50.61
72.77
76.88
77.21
77.52
126.82
127.13
128.83
129.54
129.75
135.73
138.55
143.04Current Data Parameters
NAME inn-gopi-br3-im-15-APTEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20130505Time 1.05INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG jmodTD 65536SOLVENT CDCl3NS 98DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.8 KCNST2 145.0000000CNST11 1.0000000D1 1.00000000 secd20 0.00689655 secDELTA 0.00001114 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecp2 17.50 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127538 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
37
Fig S34. 1H NMR Spectrum of 10d
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm
1.07
1.55
0.53
1.14
0.50
0.53
0.54
1.51
0.50
0.49
0.11
0.98
1.00
Current Data ParametersNAME INN-GOPI-BR3-IM-11-1HEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20130425Time 21.48INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 32DW 60.800 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
HN
CBr3
Ts
10d
38
Fig S35. 13C NMR Spectrum of 10d 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
21.73
25.86
26.17
26.74
29.54
34.01
41.43
50.63
74.37
76.88
77.20
77.52
127.61
129.60
138.27
143.79Current Data Parameters
NAME INN-GOPI-BR3-IM-11-13CEXPNO 5PROCNO 1
F2 - Acquisition ParametersDate_ 20130425Time 21.50INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 70DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secd11 0.03000000 secDELTA 0.89999998 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 WPLW13 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127562 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
HN
CBr3
Ts
10d
39
Fig S36. 13C-APT NMR Spectrum of 10d 2030405060708090100110120130140150160170180190 ppm
21.72
25.86
26.17
26.75
29.54
34.01
41.44
50.62
74.38
76.88
77.20
77.52
127.62
129.59
138.28
143.79Current Data Parameters
NAME INN-GOPI-BR3-IM-11-APTEXPNO 6PROCNO 1
F2 - Acquisition ParametersDate_ 20130425Time 21.54INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG jmodTD 65536SOLVENT CDCl3NS 69DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.9 KCNST2 145.0000000CNST11 1.0000000D1 1.00000000 secd20 0.00689655 secDELTA 0.00001114 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecp2 17.50 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127560 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
HN
CBr3
Ts
10d
40
Fig S37. 1H NMR Spectrum of 10e
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm
1.54
2.04
0.53
0.07
0.53
1.48
0.50
0.49
1.02
1.00
Current Data ParametersNAME INN-GOPI-BR3-IM-12-1HEXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20130425Time 21.38INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 11DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 32DW 60.800 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
HN
CBr3
Ts
10e
41
Fig S38. 13C NMR Spectrum of 10e 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.90
21.66
22.35
28.26
34.18
51.41
71.14
76.88
77.20
77.52
127.28
129.50
138.77
143.58Current Data Parameters
NAME INN-GOPI-BR3-IM-12-13CEXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20130425Time 21.40INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 66DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.6 KD1 1.00000000 secd11 0.03000000 secDELTA 0.89999998 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 WPLW13 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127607 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
HN
CBr3
Ts
10e
42
Fig S39. 13C-APT NMR Spectrum of 10e 2030405060708090100110120130140150160170180190 ppm
13.81
21.57
22.26
28.18
34.11
51.31
71.06
76.79
77.11
77.43
127.20
129.42
138.69
143.49Current Data Parameters
NAME INN-GOPI-BR3-IM-12-APTEXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20130425Time 21.43INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG jmodTD 65536SOLVENT CDCl3NS 46DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.9 KCNST2 145.0000000CNST11 1.0000000D1 1.00000000 secd20 0.00689655 secDELTA 0.00001114 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecp2 17.50 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127690 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
HN
CBr3
Ts
10e
43
Fig S40. 1H NMR Spectrum of 10f
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm
1.54
1.00
0.48
0.05
0.98
1.00
Current Data ParametersNAME inn-gopi-br3-im-13-1hEXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20130428Time 18.07INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 7DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 32DW 60.800 usecDE 6.50 usecTE 293.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
HN
CBr3
Ts
10f
44
Fig S41. 13C NMR Spectrum of 10f 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
21.73
40.15
64.25
76.88
77.20
77.52
127.21
130.00
137.28
144.19Current Data Parameters
NAME inn-gopi-br3-im-13-13cEXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20130428Time 18.08INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 49DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 293.2 KD1 1.00000000 secd11 0.03000000 secDELTA 0.89999998 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 WPLW13 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127615 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
HN
CBr3
Ts
10f
45
Fig S42. 13C-APT NMR Spectrum of 10f 2030405060708090100110120130140150160170180190 ppm
21.73
40.15
64.26
76.88
77.20
77.52
127.22
130.00
137.29
144.19Current Data Parameters
NAME inn-gopi-br3-im-13-aptEXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20130428Time 18.10INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG jmodTD 65536SOLVENT CDCl3NS 53DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 293.6 KCNST2 145.0000000CNST11 1.0000000D1 1.00000000 secd20 0.00689655 secDELTA 0.00001114 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecp2 17.50 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127610 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
HN
CBr3
Ts
10f
46
Fig S43. 1H NMR Spectrum of 12a
10 9 8 7 6 5 4 3 2 1 ppm
0.05
4.48
0.43
0.43
0.08
1.51
1.00
NAME INN-GOPI-BOC-1-1HEXPNO 15PROCNO 1Date_ 20111001Time 17.11INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 54DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 32DW 60.800 usecDE 6.50 usecTE 294.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
HNBoc
12a
47
Fig S44. 13C NMR Spectrum of 12a 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
28.43
50.73
70.01
76.88
77.20
77.51
80.98
128.04
129.11
129.85
135.89
154.34Current Data Parameters
NAME INN-GOPI-BOC-1-13CEXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20131128Time 2.43INSTRUM spectPROBHD 5 mm SEI 1H/D-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 374DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 296.3 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127586 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
CBr3
HNBoc
12a
48
Fig S45. 1H NMR Spectrum of 12b
10 9 8 7 6 5 4 3 2 1 ppm
0.11
4.58
0.26
1.51
0.48
0.44
0.99
0.16
1.00
NAME inn-gopi-boc 3-1hEXPNO 1PROCNO 1Date_ 20111123Time 1.51INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 28DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 32DW 60.800 usecDE 6.50 usecTE 293.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
49
Fig S46. 13C NMR Spectrum of 12b 200 180 160 140 120 100 80 60 40 20 0 ppm
21.41
28.44
51.43
69.79
76.88
77.20
77.52
80.89
128.76
129.72
132.92
139.09
154.34
NAME inn-gopi-boc 3-13cEXPNO 1PROCNO 1Date_ 20111123Time 2.42INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 69DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 293.5 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127579 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
50
Fig S47. 1H NMR Spectrum of 12c
10 9 8 7 6 5 4 3 2 1 ppm
0.04
4.58
1.54
0.47
0.48
1.01
0.06
1.00
NAME INN-GOPI-BOC-1HEXPNO 1PROCNO 1Date_ 20111116Time 2.06INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 12DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 32DW 60.800 usecDE 6.50 usecTE 294.7 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
51
Fig S48. 13C NMR Spectrum of 12c 200 180 160 140 120 100 80 60 40 20 0 ppm
28.44
52.07
55.42
69.56
76.88
77.20
77.51
80.91
113.39
127.92
131.05
154.33
160.11
NAME INN-GOPI-BOC-13CEXPNO 1PROCNO 1Date_ 20111116Time 2.10INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 97DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 295.5 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127573 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
52
Fig S49. 1H NMR Spectrum of 12d
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm
9.14
3.00
0.96
0.87
1.94
0.45
1.99
Current Data ParametersNAME IIN-GOPI-IM-BR3-SME-1HEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20130404Time 21.38INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 8DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 114DW 60.800 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
53
Fig S50. 13C NMR Spectrum of 12d2030405060708090100110120130140150160170180190 ppm
15.45
28.42
50.94
69.64
76.88
77.19
77.51
81.03
125.45
130.17
132.33
140.11
154.29Current Data Parameters
NAME INN-GOPI-IM-SME-13CEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20130407Time 15.11INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 300DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.7 KD1 1.00000000 secd11 0.03000000 secDELTA 0.89999998 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 WPLW13 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127583 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
54
Fig S51. 1H NMR Spectrum of 12e
10 9 8 7 6 5 4 3 2 1 ppm
0.32
4.40
0.73
0.98
1.01
1.02
1.00
NAME INN-GOPI-BOC-5-1HEXPNO 6PROCNO 1Date_ 20111124Time 17.13INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 19DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 32DW 60.800 usecDE 6.50 usecTE 293.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
55
Fig S52. 13C NMR Spectrum of 12e 200 180 160 140 120 100 80 60 40 20 0 ppm
28.41
50.48
69.37
76.88
77.19
77.51
81.15
114.97
115.18
131.61
131.70
154.30
161.83
164.30
NAME INN-GOPI-BOC-5-13CEXPNO 6PROCNO 1Date_ 20111124Time 17.43INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 400DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.0 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127571 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
56
Fig S53. 13C-APT NMR Spectrum of 12e 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
28.43
50.47
69.40
76.94
81.17
115.01
115.18
131.62
131.69
131.82
154.33
162.11
164.09
Current Data ParametersNAME INN-GOPI-BOC-5-APTEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20131018Time 8.41INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG jmodTD 65536SOLVENT CDCl3NS 256DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010048 secRG 197.27DW 16.800 usecDE 6.50 usecTE 296.2 KCNST2 145.0000000CNST11 1.0000000D1 1.00000000 secD20 0.00689655 secTD0 1
======== CHANNEL f1 ========SFO1 125.7703643 MHzNUC1 13CP1 8.90 usecP2 17.80 usecPLW1 103.00000000 W
======== CHANNEL f2 ========SFO2 500.1320005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 13.00000000 WPLW12 0.34327999 W
F2 - Processing parametersSI 32768SF 125.7577717 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
57
Fig S54. 19F NMR Spectrum of 12e -200-180-160-140-120-100-80-60-40-200 ppm
-112.17
Current Data ParametersNAME INN-GOPI-BOC-5-19FEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20131201Time 8.27INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgflqnTD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767668 secRG 119.07DW 4.400 usecDE 6.50 usecTE 294.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5453180 MHzNUC1 19FP1 13.50 usecPLW1 40.00000000 W
F2 - Processing parametersSI 65536SF 470.5923770 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
58
Fig S55. 1H NMR Spectrum of 12f
10 9 8 7 6 5 4 3 2 1 ppm
0.10
9.16
0.90
0.84
0.12
1.00
1.01
1.01
1.00
NAME INN-gopi-boc-2-1hEXPNO 16PROCNO 1Date_ 20111117Time 23.02INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 12DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 32DW 60.800 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
59
Fig S56. 13C NMR Spectrum of 12f 200 180 160 140 120 100 80 60 40 20 0 ppm
28.39
47.84
69.26
76.88
77.20
77.51
81.63
124.10
124.46
128.98
136.49
137.97
147.91
154.24
NAME INN-gopi-boc-2-13cEXPNO 16PROCNO 1Date_ 20111117Time 23.03INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 206DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.5 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127558 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
60
Fig S57. 1H NMR Spectrum of 13a
10 9 8 7 6 5 4 3 2 1 ppm
0.03
0.89
0.44
0.08
1.40
1.00
NAME INN-GOPI-BOC-TFA-4-1HEXPNO 2PROCNO 1Date_ 20120430Time 1.09INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 25DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 114DW 60.800 usecDE 6.50 usecTE 292.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300098 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
NH2
13a
61
Fig S58. 13C NMR Spectrum of 13a 200 180 160 140 120 100 80 60 40 20 0 ppm
59.66
73.92
76.88
77.20
77.52
128.03
129.12
129.63
137.11
NAME INN-GOPI-BOC-TFA-4-13CEXPNO 3PROCNO 1Date_ 20120430Time 1.12INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 50DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 292.3 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127549 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
CBr3
NH2
13a
62
Fig S59. 1H NMR Spectrum of 13b
10 9 8 7 6 5 4 3 2 1 ppm
0.03
0.36
1.47
0.99
0.49
1.00
0.10
1.00
NAME INN-GOPI-BOC TFA-1HEXPNO 4PROCNO 1Date_ 20120421Time 15.35INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 11DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 90.5DW 60.800 usecDE 6.50 usecTE 294.1 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Fig S60. 13C NNMR Spectrumm of 13b
63
64
Fig S61. 1H NMR Spectrum of 13c
10 9 8 7 6 5 4 3 2 1 ppm
0.04
1.11
1.54
0.48
0.99
0.09
1.00
NAME INN-GOPI-BOC-TFA-2-1HEXPNO 1PROCNO 1Date_ 20120430Time 1.57INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 101DW 60.800 usecDE 6.50 usecTE 292.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
NH2
MeO
13c
Fig S62. 13C NMR Spectrumm of 13c
MMeO
13c
65
CBr3
NH2
66
Fig S63. 1H NMR Spectrum of 13d
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm
2.34
3.17
1.00
1.88
0.56
2.01
Current Data ParametersNAME INN-GOPI-TFA-5-1HEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20130518Time 21.21INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 10DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 32DW 60.800 usecDE 6.50 usecTE 293.4 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
NH2
MeS
13d
67
Fig S64. 13C NMR Spectrum of 13d 2030405060708090100110120130140150160170180190 ppm
15.50
59.77
73.37
76.88
77.20
77.52
125.44
129.94
133.49
139.84Current Data Parameters
NAME inn-gopi-TFA-5-13CEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20130516Time 21.57INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 31DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 294.6 KD1 1.00000000 secd11 0.03000000 secDELTA 0.89999998 secTD0 1SFO1 100.6228298 MHzNUC1 13CP1 8.75 usecPLW1 -1.00000000 WSFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 -1.00000000 WPLW12 -1.00000000 WPLW13 -1.00000000 W
F2 - Processing parametersSI 32768SF 100.6127613 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
CBr3
NH2
MeS
13d
68
Fig S65. 1H NMR Spectrum of 13e
10 9 8 7 6 5 4 3 2 1 ppm
0.16
0.95
0.49
1.02
0.18
1.00
NAME INN-GOPI-BOC-TFA-3-1HEXPNO 5PROCNO 1Date_ 20120430Time 3.19INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 8DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 161DW 60.800 usecDE 6.50 usecTE 292.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
CBr3
NH2
F13e
69
Fig S66. 13C NMR Spectrum of 13e 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
59.40
73.10
76.94
77.20
77.45
114.90
115.07
131.34
131.41
132.86
162.07
164.04
Current Data ParametersNAME INN-GOPI-TFA-13C EXPNO 4 PROCNO 1
F2 - Acquisition ParametersDate_ 20131201 Time 21.36 INSTRUM spect PROBHD 5 mm PABBO BB/ PULPROG zgpg30 TD 65536 SOLVENT CDCl3 NS 75 DS 4 SWH 29761.904 Hz FIDRES 0.454131 Hz AQ 1.1010048 sec RG 197.27 DW 16.800 usec DE 6.50 usec TE 294.4 K D1 1.00000000 sec D11 0.03000000 sec TD0 1
======== CHANNEL f1 ========SFO1 125.7703637 MHz NUC1 13C P1 8.90 usec PLW1 103.00000000 W
======== CHANNEL f2 ========SFO2 500.1320005 MHz NUC2 1H CPDPRG[2 waltz16 PCPD2 80.00 usec PLW2 13.00000000 W PLW12 0.34327999 W PLW13 0.21969999 W
F2 - Processing parametersSI 32768 SF 125.7577742 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40 No parameters
CBr3
NH2
F13e
70
Fig S67. 19F NMR Spectrum of 13e -200-180-160-140-120-100-80-60-40-200 ppm
-112.38
-112.37
-112.36
-112.35
-112.34
-112.33
-112.32
Current Data ParametersNAME INN-GOPI-TFA-19FEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20131201Time 8.12INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgflqnTD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767668 secRG 119.07DW 4.400 usecDE 6.50 usecTE 294.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5453180 MHzNUC1 19FP1 13.50 usecPLW1 40.00000000 W
F2 - Processing parametersSI 65536SF 470.5923770 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
-112.30 -112.35 ppm
-112.381
-112.370
-112.362
-112.352
-112.342
-112.335
-112.323
CBr3
NH2
F13e
71
Fig S68. 1H NMR Spectrum of 18
10 9 8 7 6 5 4 3 2 1 ppm
0.02
0.02
2.44
0.77
0.23
0.21
0.22
0.50
0.50
NAME inn-gopi-1m-hg-1-1hEXPNO 1PROCNO 1Date_ 20111207Time 2.50INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 19DS 0SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 32DW 60.800 usecDE 6.50 usecTE 294.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1324710 MHzSI 32768SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
72
Fig S69. 13C NMR Spectrum of 18 200 180 160 140 120 100 80 60 40 20 0 ppm
21.34
28.46
50.60
61.39
76.88
77.20
77.52
80.66
127.31
129.39
134.42
138.57
155.10
NAME INN-GOPI-1M-AG-1-13CEXPNO 20PROCNO 1Date_ 20111223Time 0.52INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 150DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 2050DW 20.800 usecDE 6.50 usecTE 295.2 KD1 1.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL13 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WPL13W 0.29767781 WSFO2 400.1316005 MHzSI 32768SF 100.6127556 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
73
Fig S70. 13C-APT NMR Spectrum of 18 200 180 160 140 120 100 80 60 40 20 0 ppm
21.33
28.45
50.63
61.39
76.88
77.20
77.52
80.65
127.29
129.37
134.39
138.55
155.09
Current Data ParametersNAME INN-GOPI-IM-AG-1-1HEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20120318Time 11.07INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG jmodTD 65536SOLVENT CDCl3NS 400DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.50 usecTE 291.9 KCNST2 145.0000000CNST11 1.0000000D1 1.00000000 secD20 0.00689655 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.75 usecP2 17.50 usecPL1 -2.00 dBPL1W 56.53121948 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -1.00 dBPL12 14.50 dBPL2W 10.56200695 WPL12W 0.29767781 WSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127580 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
74
Figure S71. 1H-1H COSY NMR Spectrum of 18
ppm
1.01.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm
1
2
3
4
5
6
7
Current Data ParametersNAME INN-GOPI-IM-AG-1-COSYEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20111224Time 10.55INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG cosygpqfTD 2048SOLVENT CDCl3NS 16DS 16SWH 2934.272 HzFIDRES 1.432750 HzAQ 0.3489792 secRG 128DW 170.400 usecDE 6.50 usecTE 295.1 KD0 0.00000300 secD1 1.00000000 secD13 0.00000400 secD16 0.00020000 secIN0 0.00034080 sec
======== CHANNEL f1 ========NUC1 1HP0 13.50 usecP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1316350 MHz
====== GRADIENT CHANNEL =====GPNAM[1] SINE.100GPZ1 10.00 %P16 1000.00 usec
F1 - Acquisition parametersTD 264SFO1 400.1316 MHzFIDRES 11.114717 HzSW 7.333 ppmFnMODE QF
F2 - Processing parametersSI 2048SF 400.1300095 MHzWDW SINESSB 0LB 0 HzGB 0PC 1.40
F1 - Processing parametersSI 512MC2 QFSF 400.1300095 MHzWDW SINESSB 0LB 0 HzGB 0
75
Figure S72. 1H-1H COSY NMR Expansion Spectrum of 18
ppm
5.15.25.35.45.55.65.75.85.96.06.16.2 ppm
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
Current Data ParametersNAME INN-GOPI-IM-AG-1-COSYEXPNO 4PROCNO 1
F2 - Acquisition ParametersDate_ 20111224Time 10.55INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG cosygpqfTD 2048SOLVENT CDCl3NS 16DS 16SWH 2934.272 HzFIDRES 1.432750 HzAQ 0.3489792 secRG 128DW 170.400 usecDE 6.50 usecTE 295.1 KD0 0.00000300 secD1 1.00000000 secD13 0.00000400 secD16 0.00020000 secIN0 0.00034080 sec
======== CHANNEL f1 ========NUC1 1HP0 13.50 usecP1 13.50 usecPL1 -1.00 dBPL1W 10.56200695 WSFO1 400.1316350 MHz
====== GRADIENT CHANNEL =====GPNAM[1] SINE.100GPZ1 10.00 %P16 1000.00 usec
F1 - Acquisition parametersTD 264SFO1 400.1316 MHzFIDRES 11.114717 HzSW 7.333 ppmFnMODE QF
F2 - Processing parametersSI 2048SF 400.1300095 MHzWDW SINESSB 0LB 0 HzGB 0PC 1.40
F1 - Processing parametersSI 512MC2 QFSF 400.1300095 MHzWDW SINESSB 0LB 0 HzGB 0
