The Journal of Organic Chemistry
Article
2-Methyl-3-phenyl-1H-pyrrolo[3,2-c]pyridine 28a and 3-
Methyl-2-phenyl-1H-pyrrolo[3,2-c]pyridine 28b. Compounds
28a and 28b were prepared following the general procedure A with
201 mg (0.767 mmol) of 4-acetamido-3-iodopyridine 1 and 286 μL
(2.302 mmol) of propynylbenzene. The purification of the residue by
chromatography (silica gel, cyclohexane/EtOAc/MeOH 70:30:0 to
0:90:10) gave a mixture of 28a and 28b (132 mg, 83% yield) as a
MeOH 70:30:0 to 0:90:10) gave a mixture of 31a and 31b (176 mg,
92% yield) as a white solid. Rf = 0.31 (EtOAc/MeOH 9/1). 31a. H
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NMR (DMSO, 300 MHz), δ (ppm): 11.60 (s br, 1H), 8.73 (s, 1H),
8.18 (d br, 1H), 7.61−7.47 (m, 6H), 2.72 (d, J = 7.2 Hz, 2H), 2.12−
2.01 (m, 1H), 0.82 (d, J = 6.0 Hz, 6H). 13C NMR (DMSO, 75 MHz),
δ (ppm): 141.2, 140.7, 139.6, 137.4, 134.9, 132.0, 129.6 (2C), 129.2
(2C), 128.2, 113.2, 106.8, 35.3, 28.8, 22.7 (2C). IR (CH2Cl2), ν
(cm−1): 3451, 3045, 2959, 2869, 1605, 1468, 1172, 770, 751, 670.
LRMS (ESI+): m/z = 251.1 ([M + H]+, 100). HRMS (ESI+): calcd for
C17H18N2 [M + H]+: 251.1548, found 251.1547. 31b. 1H NMR
(DMSO, 300 MHz), δ (ppm): 11.67 (s br, 1H), 8.87 (s, 1H), 8.18 (s
br, 1H), 7.61−7.47 (m, 6H), 2.78 (d, J = 7.2 Hz, 2H), 2.01−1.88 (m,
1H), 0.84 (d, J = 6.3 Hz, 6H). 13C NMR (DMSO, 75 MHz), δ (ppm):
142.6, 140.4, 139.4, 135.9, 133.0, 131.9, 129.2 (2C), 128.6 (2C), 126.5,
111.4, 106.8, 33.4, 30.1, 23.0 (2C).
2-Isopropyl-3-phenyl-1H-pyrrolo[3,2-c]pyridine 32a and 3-
Isopropyl-2-phenyl-1H-pyrrolo[3,2-c]pyridine 32b. Compounds
32a and 32b were prepared following the general procedure A with
202 mg (0.771 mmol) of 4-acetamido-3-iodopyridine 1 and 333 mg
(2.313 mmol) of (3-methylbut-1-ynyl)benzene. The purification of the
residue by chromatography (silica gel, cyclohexane/EtOAc/MeOH
70:30:0 to 0:90:10) gave a mixture of 32a and 32b (150 mg, 83%
yield) as a white solid. Rf = 0.18 (EtOAc/MeOH 9/1). 32a. 1H NMR
(DMSO, 300 MHz), δ (ppm): 11.57 (s br, 1H), 8.68 (s, 1H), 8.14 (d,
J = 5.1 Hz, 1H), 7.55−7.29 (m, 5H), 7.30 (d, J = 5.1 Hz, 1H), 3.28 (st,
J = 7.1 Hz, 1H), 1.31 (d, J = 7.1 Hz, 6H). 13C NMR (DMSO, 75
MHz), δ (ppm): 144.2, 141.4, 140.6, 140.0, 133.1, 129.7 (2C), 129.5
(2C), 127.1, 124.6, 111.4, 107.4, 26.1, 23.4 (2C). IR (CH2Cl2), ν
(cm−1): 3452, 3047, 2967, 2360, 1469, 745, 729, 698. LRMS (ESI+):
m/z = 237.1 ([M + H]+, 100). HRMS (ESI+): calcd for C16H17N2 [M
+ H]+ 237.1392, found 237.1381. 32b. 1H NMR (DMSO, 300 MHz),
δ (ppm): 11.52 (s br, 1H), 9.02 (s, 1H), 8.15 (d, J = 5.1 Hz, 1H),
7.55−7.29 (m, 5H), 7.33 (d, J = 5.1 Hz, 1H), 3.29 (st, J = 7.1 Hz, 1H),
1.41 (d, J = 7.1 Hz, 6H). 13C NMR (DMSO, 75 MHz), δ (ppm):
143.4, 140.6, 140.4, 135.1, 134.9, 130.1 (2C), 129.7 (2C), 128.9, 124.8,
118.7, 107.7, 26.2, 24.4 (2C).
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white solid. Rf = 0.17 (EtOAc/MeOH 9/1). 28a. H NMR (DMSO,
300 MHz), δ (ppm): 11.63 (s br, 1H), 8.79 (s, 1H), 8.16 (d, J = 5.0
Hz, 1H), 7.5667.37 (m, 5H), 7.33 (d, J = 5.0 Hz, 1H), 2.48 (s, 3H).
13C NMR (DMSO, 75 MHz), δ (ppm): 142.7, 141.5, 141.4, 139.6,
134.4, 129.6 (2C), 128.5 (2C), 126.7, 124.8, 112.7, 107.0, 13.1. IR
(CH2Cl2), ν (cm−1): 3451, 3046, 2974, 2361, 1469, 744, 728, 605.
LRMS (ESI+): m/z = 209.1 ([M + H]+, 100). HRMS (ESI+): calcd for
C14H13N2 [M + H]+: 209.1079, found 209.1071. 28b. 1H NMR
(DMSO, 300 MHz), δ (ppm): 11.63 (s br, 1H), 8.84 (s, 1H), 8.18 (d,
J = 5.0 Hz, 1H), 7.69 (d, J = 7.5 Hz, 2H), 7.56−7.37 (m, 3H), 7.31 (d,
J = 5.0 Hz, 1H), 2.46 (s, 3H). 13C NMR (DMSO, 75 MHz), δ (ppm):
142.7, 140.9, 140.0, 135.5, 135.2, 133.0, 129.7 (2C), 128.7 (2C), 127.1,
107.4, 107.1, 10.4.
2-Butyl-3-phenyl-1H-pyrrolo[3,2-c]pyridine 29a and 3-Butyl-
2-phenyl-1H-pyrrolo[3,2-c]pyridine 29b. Compounds 29a and
29b were prepared following the general procedure A with 202 mg
(0.771 mmol) of 4-acetamido-3-iodopyridine 1 and 363 mg (2.313
mmol) of hex-1-ynylbenzene. The purification of the residue by
chromatography (silica gel, cyclohexane/EtOAc/MeOH 70:30:0 to
0:90:10) gave a mixture of 29a and 29b (156 mg, 81% yield) as a
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white solid. Rf = 0.16 (EtOAc/MeOH 9/1). 29a. H NMR (DMSO,
300 MHz), δ (ppm): 11.62 (s br, 1H), 8.74 (s, 1H), 8.17 (s br, 1H),
7.53−7.47 (m, 5H), 7.31 (s br, 1H), 2.82 (t, J = 8.1 Hz, 2H), 1.74−
1.62 (m, 2H), 1.35−1.24 (m, 2H), 0.84 (t, J = 7.5 Hz, 3H). 13C NMR
(DMSO, 75 MHz), δ (ppm): 140.3, 139.6, 138.9, 137.5, 133.9, 128.7
(2C), 128.4 (2C), 125.7, 123.7, 111.6, 105.9, 30.9, 25.1, 21.6, 13.2. IR
(CH2Cl2), ν (cm−1): 3450, 3048, 2961, 2932, 1468, 751, 714, 698.
LRMS (ESI+): m/z = 251.2 ([M + H]+, 100). HRMS (ESI+): calcd for
C17H19N2 [M + H]+ 251.1548, found 251.1545. 29b. 1H NMR
(DMSO, 300 MHz), δ (ppm): 11.62 (s br, 1H), 8.86 (s, 1H), 8.17 (s
br, 1H), 7.53−7.47 (m, 5H), 7.32 (s br, 1H), 2.88 (t, J = 7.5 Hz, 2H),
1.70−1.58 (m, 2H), 1.41−1.27 (m, 2H), 0.87 (t, J = 7.5 Hz, 3H). 13C
NMR (DMSO, 75 MHz), δ (ppm): 141.4, 139.9, 138.9, 134.5, 131.9,
128.5 (2C), 127.6 (2C), 125.7, 123.9, 111.6, 106.0, 32.6, 23.2, 21.2,
13.4.
2-Cyclohexyl-3-phenyl-1H-pyrrolo[3,2-c]pyridine 33a and 3-
Cyclohexyl-2-phenyl-1H-pyrrolo[3,2-c]pyridine 33b. Com-
pounds 33a and 33b were prepared following the general procedure
A with 238 mg (0.908 mmol) of 4-acetamido-3-iodopyridine 1 and
501 mg (2.725 mmol) of (cyclohexylethynyl)benzene. The
purification of the residue by chromatography (silica gel, cyclo-
hexane/EtOAc/MeOH 70:30:0 to 0:90:10) gave a mixture of 33a and
33b (242.3 mg, 94% yield) as a white solid. 33a. Rf = 0.19 (EtOAc/
2-(Methoxymethyl)-3-phenyl-1H-pyrrolo[3,2-c]pyridine 30a
and 3-(Methoxymethyl)-2-phenyl-1H-pyrrolo[3,2-c]pyridine
30b. Compounds 30a and 30b were prepared following the general
procedure A with 223 mg (0.851 mmol) of 4-acetamido-3-
iodopyridine 1 and 373 mg (2.553 mmol) of (3-methoxyprop-1-
ynyl)benzene. The purification of the residue by chromatography
(silica gel, cyclohexane/EtOAc/MeOH 70:30:0 to 0:90:10) gave a
mixture of 30a and 30b (157 mg, 77% yield) as a white solid. 30a. Rf =
1
MeOH 9/1). H NMR (DMSO, 300 MHz), δ (ppm): 11.79 (s br,
1H), 8.68 (s, 1H), 8.13 (d br, 1H), 7.52−7.35 (m, 5H), 7.33 (d br, J =
3.6 Hz, 1H), 2.97−2.81 (m, 1H), 1.88−1.62 (m, 7H), 1.39−1.24 (m,
3H). 13C NMR (DMSO, 75 MHz), δ (ppm): 142.1, 140.5, 138.8,
138.6, 134.0, 128.9 (2C), 128.4 (2C), 125.8, 123.8, 110.2, 106.0, 35.0,
32.1 (2C), 25.8 (2C), 25.1. IR (CH2Cl2), ν (cm−1): 3450, 3049, 2931,
2854, 2360, 1467, 744, 714, 698. LRMS (ESI+): m/z = 277.2 ([M +
H]+, 100). HRMS (ESI+): calcd for C19H21N2 [M + H]+: 277.1705,
found 277.1698. 33b. Rf = 0.23 (EtOAc/MeOH 9/1). 1H NMR
(DMSO, 300 MHz), δ (ppm): 11.79 (s br, 1H), 9.06 (s, 1H), 8.13 (d
br, 1H), 7.54−7.38 (m, 5H), 7.33 (d br, 1H), 2.97−2.81 (m, 1H),
2.03−1.92 (m, 2H), 1.83−1.61 (m, 5H), 1.40−1.25 (m, 3H). 13C
NMR (DMSO, 75 MHz), δ (ppm): 142.7, 142.1, 139.3, 134.0, 132.1,
128.4 (4C), 127.6, 123.8, 116.6, 106.4, 35.5, 33.0 (2C), 26.3 (2C),
25.2.
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0.29 (EtOAc/MeOH 9/1). H NMR (DMSO, 300 MHz), δ (ppm):
11.91 (s br, 1H), 8.89 (s, 1H), 8.23 (d, J = 5.5 Hz, 1H), 7.56−7.43 (m,
4H), 7.38 (d, J = 5.5 Hz, 1H), 7.33 (t, J = 7.0 Hz, 1H), 4.59 (s, 2H),
3.33 (s, 3H). 13C NMR (DMSO, 75 MHz), δ (ppm): 142.0, 140.7,
139.1, 133.5, 133.2, 129.0 (2C), 128.8 (2C), 126.4, 123.3, 114.3, 106.7,
65.1, 57.7. IR (CH2Cl2), ν (cm−1): 3664, 3051, 2981, 1627, 1270, 724,
712, 704. LRMS (ESI+): m/z = 239.1 ([M + H]+, 100). HRMS (ESI+):
calcd for C15H15N2O [M + H]+: 239.1184, found 239.1175. 30b. Rf =
1
0.21 (EtOAc/MeOH 9/1). H NMR (DMSO, 300 MHz), δ (ppm):
11.93 (s br, 1H), 8.97 (s br, 1H), 8.23 (s, 1H), 7.73 (d, J = 7.5 Hz,
2H), 7.56 (t, J = 7.5 Hz, 2H), 7.46 (d, J = 7.5 Hz, 1H), 7.42 (d, J = 4.8
Hz, 1H), 4.65 (s, 2H), 3.35 (s, 3H). 13C NMR (DMSO, 75 MHz), δ
(ppm): 141.9, 140.7, 139.1, 137.9, 131.2, 128.9 (2C), 128.3, 128.1
(2C), 125.8, 108.2, 106.5, 64.2, 57.1.
2-Isobutyl-3-phenyl-1H-pyrrolo[3,2-c]pyridine 31a and 3-
Isobutyl-2-phenyl-1H-pyrrolo[3,2-c]pyridine 31b. Compounds
31a and 31b were prepared following the general procedure A with
203 mg (0.775 mmol) of 4-acetamido-3-iodopyridine 1 and 367 mg
(2.324 mmol) of (4-methylpent-1-ynyl)benzene. The purification of
the residue by chromatography (silica gel, Cyclohexane/EtOAc/
2-Cyclopropyl-3-phenyl-1H-pyrrolo[3,2-c]pyridine 34a and
3-Cyclopropyl-2-phenyl-1H-pyrrolo[3,2-c]pyridine 34b. Com-
pounds 34a and 34b were prepared following the general procedure A
with 200 mg (0.763 mmol) of 4-acetamido-3-iodopyridine 1 and 327
mg (2.290 mmol) of (cyclopropylethynyl)benzene. The purification of
the residue by chromatography (silica gel, Cyclohexane/EtOAc/
MeOH 70:30:0 to 0:90:10) gave a mixture of 34a and 34b (136 mg,
1
76% yield) as a white solid. Rf = 0.25 (EtOAc/MeOH 9/1). 34a. H
NMR (DMSO, 300 MHz), δ (ppm): 11.60 (s br, 1H), 8.86 (s, 1H),
8.13 (d, J = 5.1 Hz, 1H), 7,82 (d, J = 7.5 Hz, 2H), 7,51 (t, J = 7.5 Hz,
2H), 7,38 (t, J = 7.5 Hz, 1H), 7.29 (d, J = 5.1 Hz, 1H), 2.13−2.03 (m,
H
dx.doi.org/10.1021/jo300481s | J. Org. Chem. XXXX, XXX, XXX−XXX