Page 7 of 15
The Journal of Organic Chemistry
(dd, J 7.3, 7.3 Hz, 1H), 7.25 (dd, J 7.6, 7.2 Hz, 2H), 8.11 2H), 3.73 (d, J 10.1 Hz, 1H), 3.98 (d, J 10.1 Hz, 1H), 7.09
(d, J 8.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) 171.2,
141.9, 140.2, 138.7, 133.3, 128.5, 128.4, 128.2, 125.9, 122.9,
116.7, 60.6, 43.6, 43.4, 36.0, 31.9, 31.1, 29.7, 29.64, 29.56,
29.53, 29.46, 29.4, 27.1, 24.7, 22.7, 21.2, 14.1; HRMS (ESI-
TOF) Calcd for C30H44NO ([MH]) 434.3417. Found
434.3419.
(d, J 2.1 Hz, 1H), 7.12 (d, J 7.0 Hz, 2H), 7.15-7.20 (m, 2H),
7.25-7.27 (m, 2H), 7.30 (d, J 8.5 Hz, 1H); 13C{1H} NMR
(100 MHz, CDCl3) 141.3, 140.4, 140.1, 128.54, 128.45,
128.20, 128.18, 126.1, 123.6, 114.1, 62.0, 44.2, 43.9, 42.8,
31.0, 26.5, 7.8; HRMS (ESI-TOF) Calcd for C19H23ClNO2S
([MH]) 364.1133. Found 364.1131.
1
2
3
4
5
6
7
8
9
2d4,
1-(3,5-dimethyl-3-phenethylindolin-1-
isolated by flash column
2g,
1-(4,6-dichloro-3-methyl-3-phenethylindolin-1-
yl)octadecan-1-one,
yl)octan-1-one, isolated by flash column chromatography
(petroleum ether/ethyl acetate 100:1) in 41% yield (44
mg), colorless oil. 1H NMR (400 MHz, CDCl3) 0.89 (t, J
7.0 Hz, 3H), 1.30-1.37 (m, 8H), 1.52 (s, 3H), 1.67-1.74 (m,
2H), 1.89-1.99 (m, 1H), 2.24-2.51 (m, 5H), 3.70 (d, J 10.3
Hz, 1H), 3.93 (d, J 10.3 Hz, 1H), 7.01 (d, J 1.8 Hz, 1H),
7.11 (d, J 7.0 Hz, 2H), 7.17 (dd, J 7.3, 7.3 Hz, 1H), 7.26
(dd, J 7.3, 7.3 Hz, 2H), 8.31 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3) 171.8, 145.3, 141.4, 134.4, 132.0, 130.4,
128.5, 128.3, 126.1, 124.7, 116.0, 60.8, 45.3, 40.3, 36.1,
31.7, 31.5, 29.3, 29.2, 26.4, 24.4, 22.7, 14.1; HRMS (ESI-TOF)
Calcd for C25H32Cl2NO ([MH]) 432.1855. Found
432.1871.
chromatography (petroleum ether/ethyl acetate 95:1) in
57% yield (74 mg), colorless oil. 1H NMR (400 MHz, CDCl3)
0.88 (t, J 7.0 Hz, 3H), 1.25-1.36 (m, 28H), 1.40 (s, 3H),
1.68-1.75 (m, 2H), 1.87-2.00 (m, 2H), 2.29-2.49 (m, 6H),
2.52-2.60 (m, 1H), 3.68 (d, J 10.3 Hz, 1H), 3.89 (d, J 10.3
Hz, 1H), 6.92 (s, 1H), 7.03 (d, J 8.4 Hz, 1H), 7.11 (d, J 7.0
Hz, 2H), 7.16 (dd, J 7.3, 7.3 Hz, 1H), 7.25 (dd, J 7.6, 7.1
Hz, 2H), 8.11 (d, J 8.2 Hz, 1H); 13C{1H} NMR (100 MHz,
CDCl3) 171.1, 141.9, 140.2, 138.7, 133.3, 128.5, 128.4,
128.2, 125.9, 122.9, 116.7, 60.6, 43.6, 43.4, 36.0, 31.9, 31.1,
29.71, 29.67, 29.6, 29.52, 29.46, 29.4, 27.1, 24.7, 22.7, 21.2,
14.1; HRMS (ESI-TOF) Calcd for C36H56NO ([MH])
518.4356. Found 518.4352.
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
2h1, 1-(3,5-dimethyl-3-(2-methylphenethyl)indolin-1-
yl)octan-1-one, isolated by flash column chromatography
(petroleum ether/ethyl acetate 50:1) in 62% yield (61
mg), pale yellow oil. 1H NMR (400 MHz, CDCl3) 0.88 (t, J
7.0 Hz, 3H), 1.30-1.40 (m, 8H), 1.41 (s, 3H), 1.68-1.78 (m,
2H), 1.80-1.91 (m, 2H), 2.20 (s, 3H), 2.27-2.42 (m, 6H),
2.52-2.59 (m, 1H), 3.73 (d, J 10.3 Hz, 1H), 3.95 (d, J 10.3
Hz, 1H), 6.94 (s, 1H), 6.99-7.12 (m, 5H), 8.12 (d, J 8.2 Hz,
1H); 13C{1H} NMR (100 MHz, CDCl3) 171.1, 140.2, 140.0,
138.7, 135.6, 133.3, 130.3, 128.7, 128.5, 126.1, 122.9, 116.8,
60.6, 43.6, 42.2, 36.0, 31.8, 29.4, 29.2, 28.4, 26.9, 24.7, 22.7,
21.2, 19.1, 14.1; HRMS (ESI-TOF) Calcd for C27H38NO
([MH]) 392.2948. Found 392.2949.
2d5,
1-(3,5-dimethyl-3-phenethylindolin-1-yl)-2,2-
dimethylpropan-1-one, isolated by flash column
chromatography (petroleum ether/ethyl acetate 60:1) in
60% yield (50 mg), white solid: mp 59-60 C. 1H NMR (400
MHz, CDCl3) 1.36 (s, 9H), 1.38 (s, 3H), 1.84-1.99 (m, 2H),
2.33 (s, 3H), 2.44-2.51 (m, 1H), 2.59-2.66 (m, 1H), 3.85 (d, J
10.2 Hz, 1H), 4.11 (d, J 10.2 Hz, 1H), 6.93 (s, 1H), 7.02
(d, J 7.8 Hz, 1H), 7.11 (d, J 7.2 Hz, 2H), 7.16 (dd, J 7.4,
7.2 Hz, 1H), 7.25 (dd, J 7.7, 7.0 Hz, 2H), 8.10 (d, J 8.2 Hz,
1H); 13C{1H} NMR (100 MHz, CDCl3) 176.1, 141.9, 141.6,
138.5, 133.4, 128.5, 128.3, 128.2, 126.0, 122.6, 118.2, 61.9,
44.2, 42.5, 40.1, 31.2, 27.7, 25.4, 21.1; HRMS (ESI-TOF)
Calcd for C23H30NO ([MH]) 336.2322. Found 336.2322.
2h2, 1-(3,5-dimethyl-3-(3-methylphenethyl)indolin-1-
yl)octan-1-one, isolated by flash column chromatography
(petroleum ether/ethyl acetate 60:1) in 51% yield (50
mg), colorless oil. 1H NMR (400 MHz, CDCl3) 0.88 (t, J
6.8 Hz, 3H), 1.30-1.39 (m, 11H), 1.68-1.75 (m, 2H), 1.86-
1.99 (m, 2H), 2.30-2.43 (m, 9H), 2.49-2.56 (m, 1H), 3.68 (d,
J 10.3 Hz, 1H), 3.89 (d, J 10.3 Hz, 1H), 6.90-7.03 (m, 5H),
7.14 (dd, J 7.8, 7.8 Hz, 1H), 8.11 (d, J 8.2 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3) 171.1, 141.8, 140.2, 138.7,
138.0, 133.3, 129.1, 128.4, 128.3, 126.7, 125.2, 122.9, 116.7,
60.6, 43.6, 43.4, 36.0, 31.8, 31.0, 29.4, 29.2, 27.1, 24.7, 22.7,
21.4, 21.2, 14.1; HRMS (ESI-TOF) Calcd for C27H38NO
([MH]) 392.2948. Found 392.2946.
2e,
tert-butyl
3,5-dimethyl-3-phenethylindoline-1-
carboxylate, 1:1 mixture of rotamers due to the slow
rotation of the N–(CO) bond, isolated by flash column
chromatography (petroleum ether/ethyl acetate 300:1)
1
in 46% yield (40 mg), colorless oil. H NMR (400 MHz,
CDCl3) 1.36 (s, 3H), 1.57 (s, 9H), 1.83-1.96 (m, 2H), 2.31
(s, 3H), 2.35-2.43 (m, 1H), 2.56-2.63 (m, 1H), 3.64 (brs, 1H),
3.86 (brs, 0.5H), 3.94 (brs, 0.5H), 6.90 (s, 1H), 6.99 (d, J
7.7 Hz, 1H), 7.12 (d, J 7.2 Hz, 2H), 7.15 (dd, J 7.3, 7.3 Hz,
1H), 7.25 (dd,
J 7.6, 7.2 Hz, 2H), 7.33 (brs,
unexchangeable, 0.5H), 7.73 (brs, unexchangeable, 0.5H);
13C{1H} NMR (100 MHz, CDCl3) 152.5 (br), 142.2, 140.0-
138.4 (brm), 131.8, 128.4, 128.3, 125.8, 123.3 (br), 123.1
(br), 114.4, 81.4 (br), 80.4 (br), 60.1 (br), 59.8 (br), 43.6,
42.9 (br), 42.2 (br), 31.0, 28.5, 27.2, 21.0; HRMS (ESI-TOF)
Calcd for C23H30NO2 ([MH]) 352.2271. Found 352.2273.
2h3, 1-(3,5-dimethyl-3-(4-methylphenethyl)indolin-1-
yl)octan-1-one, isolated by flash column chromatography
(petroleum ether/ethyl acetate 60:1) in 45% yield (44
mg), pale yellow oil. 1H NMR (400 MHz, CDCl3) 0.88 (t, J
6.8 Hz, 3H), 1.30-1.39 (m, 11H), 1.68-1.75 (m, 2H), 1.86-
1.94 (m, 2H), 2.30-2.42 (m, 9H), 2.48-2.56 (m, 1H), 3.67 (d,
J 10.3 Hz, 1H), 3.88 (d, J 10.3 Hz, 1H), 6.92 (s, 1H), 6.98-
7.07 (m, 5H), 8.11 (d, J 8.2 Hz, 1H); 13C{1H} NMR (100
MHz, CDCl3) 171.1, 140.2, 138.77, 138.75, 135.4, 133.3,
129.1, 128.4, 128.1, 122.9, 116.7, 60.6, 43.6, 43.5, 36.0,
2f,
5-chloro-1-(ethylsulfonyl)-3-methyl-3-
isolated by flash column
phenethylindoline,
chromatography (petroleum ether/ethyl acetate 30:1) in
27% yield (25 mg), colorless oil. 1H NMR (400 MHz, CDCl3)
1.41 (s, 3H), 1.42 (t, J 7.4 Hz, 3H), 1.86-2.01 (m, 2H),
2.40-2.47 (m, 1H), 2.62-2.70 (m, 1H), 3.12 (q, J 7.4 Hz,
7
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