G. Ieronimo et al. / Tetrahedron xxx (2013) 1e15
13
J¼7.6 Hz, H20þH60), 6.90 (t, 2H, J¼7.6 Hz, H30þH50), 6.77 (t, 1H,
IR (KBr, cmꢁ1):
n
¼3378, 3059, 2924, 2853, 1710, 1601, 1523, 1473,
J¼7.6 Hz, H40), 4.67 (d, 1H, J¼7.1 Hz, H1 aziridine ring), 3.97 (s, 3H,
COOMe), 3.72 (s, 3H, COOMe), 3.71 (d, 1H, J¼7.1 Hz, H7a aziridine
1445, 1327, 1264, 743, 699 cmꢁ1. Elemental analyses for C14H10BrN:
calcd (%) C 61.79, H 3.70, N 5.15, found (%) C 61.92, H 3.55, N 5.06.
Compounds 12b and 12c were characterized and spectra and
analyses are in agreement with data previously reported in
literature.40
ring). 13C NMR (CDCl3, 100 MHz):
136.7,136.0,132.7,131.3,128.5,128.4,127.8,127.5,127.3,126.7,126.4,
d
¼192.3, 172.4, 166.7, 154.1, 139.1,
123.3, 62.2, 54.8, 53.4, 52.2, 49.8. MS (CI): m/z: 428 [Mþ1]. IR (film,
cmꢁ1):
n
¼2951, 2928, 2856, 2257, 1753, 1722, 1689, 1596, 1580,
1435, 1289, 1250, 1222, 907, 733 cmꢁ1. Elemental analyses for
26H21NO5: calcd (%) C 73.06, H 4.95, N 3.28, found (%) 72.87, H 4.77,
N 3.43.
4.3.3.43. 5-Nitro-3-tosyl-1H-indole (14). Reaction time: 5 h.
Flash chromatography (hexane/ethyl acetate¼6:4). Light brown
plate, mp 204e206 ꢀC (dec), yield 31%, (98 mg, 0.31 mmol). 1H
C
NMR (400 MHz, CDCl3):
d
¼9.45 (s, 1H, NH), 8.84 (d, 1H, 4J¼2.2 Hz,
4.3.3.39. trans-Dimethyl 1-benzoyl-7-phenyl-7,7a-dihydro-1H-
H4), 8.18 (dd, 1H, 3J¼9.0 Hz, 4J¼2.2 Hz, H6), 8.05 (d, 1H, 3J¼3.0 Hz,
H2), 7.94 (d, 2H, J¼8.3 Hz, H20þH60), 7.50 (d, 1H, J¼9.0 Hz, H7), 7.32
(d, 2H, J¼8.3 Hz, H30þH50), 2.40 (s, 3H, SO2C6H4Me). 13C NMR
azirino[1,2-a]indole-4,7-dicarboxylate (9g). Reaction time: 8 h. Flash
chromatography (hexane/EtOAc¼70:30, Rf¼0.30). Orange-brown
oil, yield¼21%, (137 mg, 0.21 mmol). 1H NMR (400 MHz, CDCl3):
(CDCl3, 100 MHz):
d
¼148.6, 144.2, 143.7, 139.3, 139.0, 132.4, 130.0,
d
¼7.94 (d, 2H, J¼7.6 Hz, H200þH600), 7.80 (dd, 1H, 3J¼8.1 Hz,
127.0, 122.7, 119.5, 116.7, 112.5, 21.5 ppm. MS (CI): m/z: 317. IR (KBr,
cmꢁ1):
¼3346, 2961, 2924, 2854, 1593, 1527, 1466, 1419, 1339,
1261, 1143, 1093, 1020, 800 cmꢁ1
Elemental Analysis for
15H12N2O4S: calcd (%) C, 56.95; H, 3.82; N, 8.86, found (%) C 56.61,
H 3.97, N 8.88.
4J¼1.2 Hz, H5), 7.74 (d, 1H, J¼1.2 Hz, H3), 7.68 (d, 1H, 3J¼8.1 Hz, H6),
7.58 (t,1H, J¼7.6 Hz, H400), 7.46 (t, 2H, J¼7.6 Hz, H300þH500), 7.37e7.28
(m, 5H, H20-H30-H40-H50-H60), 4.02 (d, 1H, J¼5.2 Hz, H1 aziridine
ring), 3.88 (s, 3H, COOMe), 3.82 (s, 3H, COOMe), 3.79 (d, 1H,
n
.
C
J¼5.2 Hz, H7a aziridine ring). 13C NMR (CDCl3, 100 MHz):
¼192.5,
d
171.5, 166.4, 149.5, 144.8, 142.3, 137.0, 133.8, 130.4, 129.1, 128.7,
128.4, 127.9, 127.7, 126.7, 126.1, 122.1, 62.2, 55.3, 52.6, 52.2, 47.8. MS
4.3.3.44. 5-Nitro-1,3-ditosyl-1H-indole (15). Reaction time: 5 h.
Flash chromatography (hexane/CH2Cl2¼30:70). Colourless prism,
mp 239e240 ꢀC, yield¼25%, (118 mg, 0.25 mmol). 1H NMR
(CI): m/z: 428 [Mþ1]. IR (film, cmꢁ1):
¼2952, 2926, 2854, 2257,
n
1761, 1723, 1685, 1597, 1580, 1436, 1289, 1248, 1223, 909, 732 cmꢁ1
.
(400 MHz, CDCl3):
d
¼8.75 (d, 1H, 4J¼1.9 Hz, H4), 8.43 (s, 1H, H2),
Elemental analyses for C26H21NO5: calcd (%) C 73.06, H 4.95, N 3.28,
found (%) C 72.98, H 4.87, N 3.31.
8.28 (dd, 1H, 3J¼9.2 Hz, 4J¼1.9 Hz, H6), 8.08 (d, 1H, J¼9.2 Hz, H7),
7.95 (d, 2H, J¼8.2 Hz, H20þH60), 7.87 (d, 2H, J¼8.2 Hz, H200þH600),
7.37 (d, 4H, J¼8.2 Hz, H30þH50 and H300þH500), 2.43 (s, 6H,
4.3.3.40. Dimethyl 1-(4-nitrobenzoyl)-7-(4-nitrophenyl)-7,7a-di-
SO2C6H4Me). 13C NMR (CDCl3, 100 MHz):
d
¼147.6, 145.5, 145.4,
hydro-1H-azirino[1,2-a]indole-4,7-dicarboxylate
(9h). Reaction
138.3, 137.9, 133.9, 133.4, 131.1, 130.7, 130.1, 127.8, 125.6, 124.7, 121.6,
time: 6 h. Flash chromatography (hexane/EtOAc¼50:50, Rf¼0.26).
117.3,114.6, 22.2, 22.0 ppm. MS (CI): m/z: 471 [Mþ1]. IR (KBr, cmꢁ1):
Light orange oil, yield¼44%, (228 mg, 0.44 mmol). 1H NMR
n
¼2923, 2852, 2362, 1596, 1525, 1346, 1261, 1150, 1086, 812 cmꢁ1
.
(400 MHz, CDCl3):
d
¼8.14 (d, 1H, J¼1.5 Hz, H3), 8.03 (d, 2H,
Elemental analyses for C22H18N2O6S2: calcd (%) C 56.16, H 3.86, N
5.95, found (%) C 56.25, H 3.92, N 5.81.
J¼8.7 Hz, H300þH500), 8.02 (dd, 1H, 3J¼8.0 Hz, 4J¼1.5 Hz, H5), 7.82 (d,
2H, J¼8.8 Hz, H30þH50), 7.60 (d, 1H, J¼8.0 Hz, H6), 7.53 (d, 2H,
J¼8.7 Hz, H200þH600), 7.31 (d, 2H, J¼8.8 Hz, H20þH60), 4.73 (d, 1H,
J¼6.7 Hz, H1 aziridine ring), 3.98 (s, 3H, COOMe), 3.82 (d, 1H,
J¼6.7 Hz, H7a aziridine ring), 3.76 (s, 3H, COOMe). 13C NMR (CDCl3,
Compound 16a and compound 16b show the same spectro-
scopic data reported in literature.43
4.3.3.45. 5-Nitro-3-(pyridin-2-yl)-1H-indole
(18a). Reaction
100 MHz):
d
¼190.4, 171.0, 166.2, 153.1, 150.1, 146.9, 143.9, 139.8,
time: 5 h. Flash chromatography (CH2Cl2- EtOAc¼70:30). Orange
138.0, 132.0, 128.4, 128.0, 127.1, 127.1, 123.7, 123.5, 123.3, 59.5, 54.7,
oil, yield¼39%, (93 mg, 0.39 mmol). 1H NMR (400 MHz, CDCl3):
53.9, 52.4, 49.1. MS (CI): m/z: 518 [Mþ1]. IR (film, cmꢁ1):
n
¼2924,
d
¼9.41 (d, 1H, 4J¼2.0 Hz, H4), 8.93 (s, 1H, NH), 8.75 (d, 1H, J¼4.6 Hz,
2854, 2360,1757,1723,1690,1524,1494,1437,1349, 1291,1248, 854,
756 cmꢁ1. Elemental analyses for C26H19N3O9: calcd (%) C 60.35, H
3.70, N 8.12, found (%) C 60.48, H 3.82, N 8.00.
H60), 8.20 (dd, 1H, 3J¼9.0 Hz, 4J¼2.0 Hz, H6), 7.92 (d, 1H, J¼2.2 Hz,
H2), 7.78 (t,1H, J¼7.7 Hz, H40), 7.72 (d, 1H, J¼7.7 Hz, H30), 7.49 (d, 1H,
J¼9.0 Hz, H7), 7.22 (t, 1H, J¼6.5 Hz, H50). 1H NMR (400 MHz, DMSO-
d6):
d
¼12.33 (br, s, 1H, NH), 9.40 (d, 1H, J¼2.3 Hz, H4), 8.70 (d, 1H,
4.3.3.41. 2-Bromo-5-nitro-3-phenyl-1H-indole (11a). Reaction
time: 5 h. Flash chromatography (CH2Cl2/hexane¼70:30). Yellow
platelet, mp 180e182 ꢀC, yield¼45%, (193 mg, 0.45 mmol). 1H NMR
J¼4.2 Hz, H30), 8.42 (d,1H, J¼2.7, H2), 8.08 (dd,1H, J3¼9.0, J4¼2.3 Hz,
H6), 8.00 (d, 1H, J¼7.9 Hz, H60), 7.93 (t, 1H, J¼7 Hz, H50), 7.65 (d, 1H,
J¼9.0 Hz, H7), 7.32 (t, 1H, J¼5.8 Hz, H40). 13C NMR (CDCl3, 100 MHz):
(400 MHz, CDCl3):
d
¼8.62 (d, 1H, J¼1.9 Hz, H4), 8.59 (s,1H, NH), 8.18
d
¼148.6, 147.3, 142.1, 140.5, 138.5, 134.8, 130.4, 124.9, 121.1, 119.2,
4
(dd, 1H, 3J¼9.0 Hz, J¼1.9 Hz, H6), 7.63 (d, 2H, J¼7.4 Hz, H20þH60),
117.8, 113.0, 111.5. MS (CI): m/z: 240 [Mþ1]. IR (film, cmꢁ1):
¼3378,
n
7.56 (t, 2H, J¼7.4 Hz, H30þH50), 7.46 (t,1H, J¼7.4 Hz, H40), 7.43 (d,1H,
2923, 2330, 1611, 1548, 1505, 1454, 1344, 1320, 1114, 1055, 807,
790 cmꢁ1. Elemental analyses for C13H9N3O3: calcd (%) C 61.18, H
3.55, N 16.46, found (%) C 61.39, H 3.64, N 16.61.
J¼9.0 Hz, H7). 13C NMR (CDCl3, 100 MHz):
¼143.1, 139.2, 132.1,
d
129.7, 129.3, 128.2, 127.2, 119.9, 118.8, 116.7, 111.0, 110.8. MS (CI): m/
z: 320/318 [Mþ1]. IR (KBr, cmꢁ1):
n
¼3382, 2920, 2851, 1711, 1517,
1466, 1330, 1072, 810, 699 cmꢁ1
.
Elemental analyses for
4.3.3.46. 5-Nitro-3-(pyridin-3-yl)-1H-indol-1-ol (18b). Reaction
time: 5 h. Flash chromatography (CH2Cl2/EtOAc¼50:50). Yellow oil,
yield¼46%, (117 mg, 0.46 mmol). 1H NMR (400 MHz, DMSO-d6):
C
14H9BrN2O2: calcd (%) C 53.02, H 2.86, N 8.83, found (%) C 53.11, H
2.92, N 8.67.
d
¼12.24 (s, 1H, NeOH), 8.98 (s, 1H, H20), 8.76 (d, 1H, J¼2.0 Hz, H4),
4.3.3.42. 2-Bromo-3-phenyl-1H-indole (11b). Reaction time: 7 h.
Flash chromatography (CH2Cl2/hexane¼70:30). Yellow needles, mp
102e104 ꢀC, yield¼51%, (140 mg, 0.51 mmol). 1H NMR (400 MHz,
8.56 (d, 1H, J¼4.6 Hz, H40), 8.34 (s, 1H, H2), 8.23 (d, 1H, J¼7.9 Hz,
H60), 8.14 (dd, 1H, 3J¼9.0 Hz, 4J¼2.0 Hz, H6), 7.68 (d, 1H, J¼9.0 Hz,
H7), 7.59 (dd, 1H, 3J¼7.9 Hz, J¼4.6 Hz, H50). 13C NMR (DMSO-d6,
4
CDCl3):
d
¼8.23 (s, 1H, NH), 7.70 (d, 1H, J¼7.7 Hz, H4), 7.66 (d, 2H,
100 MHz):
d¼147.8, 147.5, 142.5, 136.8, 135.8, 130.7, 128.7, 125.3,
J¼7.5 Hz, H20þH60), 7.51 (t, 2H, J¼7.5 Hz, H30þH50), 7.41e7.37 (m,
120.7, 118.4, 117.4, 111.1, 110.6. MS (CI): m/z: 256 [Mþ1]. IR (film,
2H, H40þH7), 7.25 (t, 1H, J¼7.7 Hz, H6), 7.17 (t, 1H, J¼7.7 Hz, H5). 13C
cmꢁ1):
n
¼3375, 2924, 2331, 1610, 1548, 1503, 1459, 1342, 1319, 1110,
NMR (CDCl3, 100 MHz):
d
¼136.6, 133.9, 129.9, 129.0, 127.7, 127.3,
1053, 804, 799 cmꢁ1. Elemental analyses for C13H9N3O3: calcd (%) C
61.18, H 3.55, N 16.46, found (%) C 60.99, H 3.47, N 16.15.
123.2, 121.2, 119.5, 117.5, 111.0, 108.0. MS (CI): m/z: 275/273 [Mþ1],