Page 17 of 28
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
7.01 (10 H, m), 6.75 (2 H, d, J = 7.8 Hz), 4.89 (1 H, dd, J = 8.2 & 3.8 Hz), 3.74-3.71 (1 H, m), 2.78-2.48 (2 H, m), 2.22 (3 H, s), 2.20
(3 H, s) and 1.39 (3 H, d, J = 6.9 Hz) ppm. Minor isomer 1H NMR (400 MHz, CDCl3): = 8.10 (1 H, d, J = 7.8 Hz), 7.98 (1 H, d, J =
7.8 Hz), 7.71 (2 H, d, J = 7.9 Hz), 7.60-7.52 (1 H, m), 7.28-7.01 (10 H, m), 6.83 (2 H, d, J = 7.8 Hz), 4.82 (1 H, dd, J = 8.2 & 3.8 Hz),
3.35-3.23 (1 H, m), 2.78-2.48 (2 H, m), 2.31 (3 H, s), 2.23 (3 H, s) and 1.29 (3 H, d, J = 6.9 Hz) ppm. 13C{1H} NMR (100 MHz,
CDCl3): (Major isomer) = 144.8, 144.4, 142.8, 140.8, 135.6, 135.5, 135.2, 131.7, 129.9, 129.4, 127.0, 126.7, 126.3, 126.2, 124.9,
124.4, 124.0, 123.7, 123.4, 123.2, 123.1, 119.8, 119.4, 114.9, 113.7, 47.0, 37.4, 32.3, 21.6, 21.5 and 20.5 ppm. IR (neat): 2923,
1639, 1599, 1531, 1509, 1457, 1417, 1380, 1257, 1175, 1030, 978, 884, 815, 667, 594 and 522 cm-1. HRMS (ESI-TOF) m/z:
[M+Na]+ Calcd for C34H30N2NaO4S2, 617.1539; found 617.1527.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1-(3-(4-Acetyl-1-methyl-1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)-1H-indol-1-yl)ethan-1-one (5m)
The indole-3-carbinol22b 1m (40 mg, 0.2 mmol), alkyne 2a (71 mg, 0.4 mmol), FeCl3 (16 mg, 0.098 mmol) in 1,2-DCE (5 mL) were
stirred for 5 h at 55 °C to rt. Purification by flash column chromatography (9:1 hexane:EtOAc) gave the homodimer product as
diastereomeric mixture (1:0.48) 5m (24 mg, 0.064 mmol, 65%) as a pale yellow semisolid. Rf = 0.35 (9:1, Hex/EtOAc). Major
diastereomer 1H NMR (400 MHz, CDCl3): = 8.46 (2 H, m), 7.52-7.25 (6 H, m), 6.86 (1 H, s), 4.79 (1 H, d, J = 8.03 Hz), 3.45-3.46
(1 H, m), 2.70-2.55 (2 H, m), 2.47 (3 H, s), 2.38 (3 H, s) and 1.32 (3 H, d, J = 6.8 Hz) ppm. Minor diastereomer 1H NMR (400 MHz,
CDCl3): = 8.46 (2 H, m), 7.52-7.25 (6 H, m), 6.72 (1 H, s), 4.82 (1 H, d, J = 8.03 Hz), 3.45-3.46 (1 H, m), 2.70-2.55 (2 H, m), 2.44
(3 H, s), 2.43 (3 H, s) and 1.46 (3 H, d, J = 6.8 Hz) ppm. 13C{1H} NMR (100 MHz, CDCl3): Major isomer) = 169.2, 168.6, 141.4,
141.3, 133.7, 132.8, 125.9, 125.0, 124.8, 123.9, 123.8, 121.4, 118.9, 118.8, 117.8, 117.1, 47.1, 45.8, 38.7, 31.8, 25.2, 24.2 and 20.1
ppm. IR (neat): 2926, 2855, 1699, 1451, 1387, 1331, 1217, 1129, 932, 771 and 669 cm-1. HRMS (ESI-TOF) m/z: [M+Na]+ Calcd for
C24H22N2NaO2, 393.1573; found 393.1559.
3-(4-Chloro-3-methylpent-3-en-2-yl)-1-tosyl-1H-indole (9)
The indole-3-carbinol 1a (40 mg, 0.13 mmol), 2-Butyne (15 mg, 0.25 mmol), FeCl3 (10 mg, 0.06 mmol), 1,2-DCE (3 mL) stirred for 5
min at 55 °C. Purification by column chromatography (19:1 hexane:EtOAc) gave vinyl- chloride derivative 9 (27 mg, 0.07 mmol,
55%) as a colorless solid diastereoisomer (E:Z isomer = 1:1). Rf = 0.35 (19:1, Hex/EtOAc). 1st Diastereomer : 1H NMR (400 MHz,
CDCl3): = 7.95-7.93 (1 H, m), 7.71 (2 H, d, J = 7.7 Hz), 7.36-7.37 (1 H, m), 7.32-7.24 (2 H, m), 7.21-7.15 (3 H, m), 4.55 (1 H, q, J =
6.6 Hz), 2.31 (6 H, s), (3 H, s), 1.44 (3 H, s) and 1.40 (3 H, d, J = 6.6 Hz) ppm. 2nd Diastereomer : 1H NMR (400 MHz, CDCl3): =
7.95-7.93 (1 H, m), 7.71 (2 H, d, J = 7.7 Hz), 7.46 (1 H, d, J = 7.6 Hz), 7.36-7.37 (1 H, m), 7.32-7.24 (1 H, m), 7.21-7.15 (3 H, m),
4.09 (1 H, q, J = 6.6 Hz), 2.31 (3 H, s), 2.10 (3 H, s), 1.40 (3 H, d, J = 6.6 Hz) and 1.33 (3 H, s) ppm. 13C{1H} NMR (100 MHz,
CDCl3) Mixture of diastereomer: = 144.9, 144.8, 135.6, 135.57, 135.3, 135.3, 133.4, 132.36, 130.9, 130.6, 129.9, 126.8, 126.4,
125.1, 124.9, 124.87, 123.6, 123.4, 123.37, 123.2, 122.9, 120.3, 119.8, 113.9, 113.7, 34.6, 34.0, 22.9, 22.3, 21.6, 17.4, 16.4, 15.2
and 13.7 ppm. IR (neat): 2967, 2927, 1599, 1484, 1454, 1365, 1237, 1217, 1187, 1155, 1091, 812, 761 and 668 cm-1. HRMS (ESI-
TOF) m/z: [M+H]+ Calcd for C21H23ClNO2S, 388.1125; found 388.1133.
3-(4-Chloro-3,4-diphenylbut-3-en-2-yl)-2-methyl-1-tosyl-1H-indole (10)
17
ACS Paragon Plus Environment