Full Paper
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3JH,H = 5.1 Hz, 3 H), 7.26 (s, 2 H), 7.22–7.15 (m, 3 H), 6.97 (d, JH,H
=
152.8, 147.0, 144.8, 137.7, 137.6 (d, JF,C = 4.4 Hz), 136.5, 135.9, 130.4
(d, JF,C = 8.3 Hz), 129.1, 128.9, 128.2, 126.8, 123.7 (d, JF,C = 2.6 Hz),
116.4 (d, JF,C = 21.4 Hz), 114.6, 114.1, 113.5 (d, JF,C = 21.9 Hz),
45.56 ppm. MS (ES+): m/z (%) = 408.0 (100) [M + H]+. HRMS (ESI)
calcd. for C21H16N3BrF 408.0512, found 408.0499.
3.6 Hz, 2 H), 5.97 (s, 1 H), 5.73 (s, 1 H), 5.19 (s, 2 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 155.7, 147.2, 145.1, 139.2, 137.3, 136.1, 135.9,
129.9, 129.0, 128.9, 128.6, 127.8, 127.2, 126.9, 122.6, 114.2, 46.6 ppm.
MS (ES+): m/z (%) = 390.1 (100) [M + H]+. HRMS (ESI) calcd. for
C
21H17N3Br 390.0606, found 390.0602.
(E)-3-Benzyl-6-bromo-2-(3-bromostyryl)-3H-imidazo[4,5-b]pyr-
idine (7j): The reaction was performed following General Procedure
(E)-3-Benzyl-6-bromo-2-(3-methoxystyryl)-3H-imidazo[4,5-b]-
pyridine (7f): The reaction was performed following General Proce- E on 3-benzyl-6-bromo-3H-imidazo[4,5-b]pyridine (3) (100 mg,
dure E on 3-benzyl-6-bromo-3H-imidazo[4,5-b]pyridine (3) (100 mg,
0.4 mmol) using (E)-1-(2-bromovinyl)-3-methoxybenzene (148 mg,
0.7 mmol) to afford the desired product as a yellow solid (87 mg,
62 %), m.p. 141–143 °C. 1H NMR (300 MHz, CDCl3): δ = 8.39 (d,
0.4 mmol) using (E)-1-bromo-3-(2-bromovinyl)benzene (182 mg,
0.7 mmol) to afford the desired product as a beige solid (104 mg,
64 %), m.p. 177–179 °C. 1H NMR (300 MHz, CDCl3): δ = 8.40 (d,
4
3
4JH,H = 1.9 Hz, 1 H), 8.15 (d, JH,H = 1.9 Hz, 1 H), 7.89 (d, JH,H
=
4
3
3
4JH,H = 1.6 Hz, 1 H), 8.14 (d, JH,H = 1.8 Hz, 1 H), 7.94 (d, JH,H
=
15.8 Hz, 1 H), 7.62 (s, 1 H), 7.47 (d, JH,H = 7.6 Hz, 1 H), 7.41 (d,
3JH,H = 7.6 Hz, 1 H), 7.35–7.26 (m, 3 H), 7.25–7.15 (m, 3 H), 6.99 (d,
3JH,H = 15.8 Hz, 1 H), 5.60 (s, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 152.7, 147.0, 144.8, 137.5, 137.3, 136.5, 135.9, 132.4, 130.5, 130.0,
129.2, 129.0, 128.2, 126.8, 126.4, 123.1, 114.6, 114.2, 45.6 ppm. MS
3
3
15.8 Hz, 1 H), 7.30 (t, JH,H = 7.8 Hz, 4 H), 7.21 (d, JH,H = 7.8 Hz, 2
H), 7.11 (d, JH,H = 7.6 Hz, 1 H), 7.02 (s, 1 H), 6.94 (d, 3JH,H = 15.6 Hz,
3
3
4
1 H), 6.90 (dd, JH,H = 8.4, JH,H = 1.8 Hz, 1 H), 5.59 (s, 2 H), 3.83 (s,
3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 159.9, 153.2, 147.0, 144.5,
139.0, 136.8, 136.6, 136.0, 130.0, 129.1, 128.8, 128.2, 126.8, 120.1, (ES+): m/z (%) = 468.0 (100) [M + H]+. HRMS (ESI) calcd. for
115.2, 114.5, 113.2, 112.9, 55.3, 45.5 ppm. MS (ES+): m/z (%) = 420.1
(100) [M + H]+. HRMS (ESI) calcd. for C22H19N3OBr 420.0711, found
420.0718.
C21H16N3Br2 467.9711, found 467.9712.
(E)-3-Benzyl-6-bromo-2-(3-nitrostyryl)-3H-imidazo[4,5-b]pyr-
idine (7k): The reaction was performed following General Proce-
dure E on 3-benzyl-6-bromo-3H-imidazo[4,5-b]pyridine (3) (100 mg,
0.4 mmol) using (E)-1-(2-bromovinyl)-3-nitrobenzene (158 mg,
(E)-3-Benzyl-2-{3,4-bis[(tert-butyldimethylsilyl)oxy]styryl}-6-
bromo-3H-imidazo[4,5-b]pyridine (7g): The reaction was per-
formed following General Procedure E on 3-benzyl-6-bromo-3H-im- 0.7 mmol) to afford the desired product as a brown solid (40 mg,
idazo[4,5-b]pyridine (3) (100 mg, 0.4 mmol) using (E)-{[4-(2-bromo- 26 %), m.p. 210–212 °C. 1H NMR (300 MHz, CDCl3): δ = 8.43 (s, 1 H),
3
vinyl)-1,2-phenylene]bis(oxy)}bis(tert-butyldimethylsilane) (308 mg,
8.34 (s, 1 H), 8.17 (s, 2 H), 8.00 (d, JH,H = 15.8 Hz, 1 H), 7.75 (d, J =
0.7 mmol) to afford the desired product as a light yellow solid
6.9 Hz, 1 H), 7.56 (t, J = 7.8 Hz, 1 H), 7.38–7.28 (m, 2 H), 7.28–7.19
3
(120 mg, 49 %), m.p. 144–146 °C. 1H NMR (300 MHz, CDCl3): δ = (m, 3 H), 7.12 (d, JH,H = 16.4 Hz, 1 H), 5.64 (s, 2 H) ppm. 13C NMR
3
8.37 (s, 1 H), 8.11 (s, 1 H), 7.85 (d, JH,H = 15.9 Hz, 1 H), 7.31–7.15
(75 MHz, CDCl3): δ = 152.2, 148.8, 147.0, 145.2, 137.2, 136.4, 136.0,
135.8, 133.5, 130.0, 129.2, 129.2, 128.4, 126.8, 123.9, 121.4, 115.9,
3
(m, 5 H), 7.03–6.93 (m, 2 H), 6.81 (d, JH,H = 6.6 Hz, 1 H), 6.76 (d,
3JH,H = 15.6 Hz, 1 H), 5.57 (s, 2 H), 0.99 (s, 9 H), 0.98 (s, 9 H), 0.21 (d, 114.8, 45.7 ppm. MS (ES+): m/z (%) = 435.0 (100) [M + H]+, 476.1
J = 2.9 Hz, 12 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 153.8, 148.9,
(10) [M + CH3CN + H]+. HRMS (ESI) calcd. for C21H16N4O2Br 435.0457,
147.2, 147.1, 144.1, 138.9, 136.6, 136.1, 129.1, 129.0, 128.4, 128.1, found 435.0462.
126.8, 121.3, 121.3, 120.1, 114.3, 110.5, 108.2, 45.5, 25.9, 25.9, 18.5,
(E)-4-[2-(3-Benzyl-6-bromo-3H-imidazo[4,5-b]pyridin-2-yl)vin-
–4.1 ppm. MS (ES+): m/z (%) = 650.2 (100) [M + H]+, 1299.4 (10)
[2M + H]+. HRMS (ESI) calcd. for C33H45N3O2BrSi2 650.2234, found
650.2226.
yl]benzonitrile (7l): The reaction was performed following General
Procedure E on 3-benzyl-6-bromo-3H-imidazo[4,5-b]pyridine (3)
(90 mg, 0.3 mmol) using (E)-4-(2-bromovinyl)benzonitrile (130 mg,
0.6 mmol) to afford the desired product as a light yellow solid
(60 mg, 47 %), m.p. 186–188 °C. 1H NMR (300 MHz, CDCl3): δ = 8.44
(E)-3-Benzyl-6-bromo-2-[4-(diethoxymethyl)styryl]-3H-imid-
azo[4,5-b]pyridine (7h): The reaction was performed following
4
4
3
General Procedure E on 3-benzyl-6-bromo-3H-imidazo[4,5-b]pyri- (d, JH,H = 1.9 Hz, 1 H), 8.18 (d, JH,H = 1.9 Hz, 1 H), 7.97 (d, JH,H
=
3
3
dine (3) (100 mg, 0.4 mmol) using (E)-1-(2-bromovinyl)-4-(diethoxy- 15.6 Hz, 1 H), 7.67 (d, JH,H = 8.6 Hz, 2 H), 7.57 (d, JH,H = 8.5 Hz, 2
methyl)benzene (198 mg, 0.7 mmol) to afford the desired product H), 7.33 (m, 2 H), 7.22 (m, 3 H), 7.08 (d, JH,H = 15.7 Hz, 1 H), 5.62
3
as a yellow solid (110 mg, 60 %), m.p. 115–117 °C. 1H NMR
(s, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 152.2, 147.0, 145.3,
139.7, 136.6, 136.5, 135.9, 132.7, 129.2, 129.2, 128.3, 127.8, 126.7,
118.5, 116.3, 114.8, 112.6, 45.6 ppm. MS (ES+): m/z (%) = 415.1 (50)
[M + H]+. HRMS (ESI) calcd. for C22H16N4Br 415.0558, found
415.0552.
4
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(300 MHz, CDCl3): δ = 8.39 (d, JH,H = 2.0 Hz, 1 H), 8.14 (d, JH,H
=
3
2.0 Hz, 1 H), 7.98 (d, JH,H = 15.8 Hz, 1 H), 7.50 (s, 4 H), 7.36–7.27
(m, 3 H), 7.24–7.18 (m, 2 H), 7.01 (d, JH,H = 15.8 Hz, 1 H), 5.59 (s, 2
3
H), 5.50 (s, 1 H), 3.81–3.28 (m, 4 H), 1.24 (t, J = 7.0 Hz, 6 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 153.3, 147.0, 144.5, 140.7, 138.7, 136.6,
136.0, 135.4, 129.1, 128.8, 128.2, 127.4, 127.3, 126.8, 114.5, 113.0,
101.1, 61.1, 45.5, 26.9, 15.2 ppm. MS (ES+): m/z (%) = 418.1 (30)
[deprotected aldehyde + H]+, 492.1 (100) [M + H]+. HRMS (ESI) calcd.
for C26H27N3O2Br 492.1287, found 492.1266.
(E)-3-Benzyl-6-bromo-2-[4-(trifluoromethyl)styryl]-3H-imid-
azo[4,5-b]pyridine (7m): The reaction was performed following
General Procedure E on 3-benzyl-6-bromo-3H-imidazo[4,5-b]pyr-
idine (3) (100 mg, 0.4 mmol) using (E)-1-(2-bromovinyl)-4-(trifluoro-
methyl)benzene (174 mg, 0.7 mmol) to afford the desired product
as a beige solid (90 mg, 60 %), m.p. 186–188 °C. 1H NMR (300 MHz,
(E)-3-Benzyl-6-bromo-2-(3-fluorostyryl)-3H-imidazo[4,5-b]pyr-
idine (7i): The reaction was performed following General Procedure
4
4
CDCl3): δ = 8.42 (d, JH,H = 2.0 Hz, 1 H), 8.16 (d, JH,H = 2.0 Hz, 1 H),
3
3
E on 3-benzyl-6-bromo-3H-imidazo[4,5-b]pyridine (3) (100 mg, 7.98 (d, JH,H = 15.8 Hz, 1 H), 7.63 (d, JH,H = 8.4 Hz, 2 H), 7.58 (d,
0.4 mmol) using (E)-1-(2-bromovinyl)-3-fluorobenzene (140 mg,
0.7 mmol) to afford the desired product as a beige solid (85 mg,
58 %), m.p. 141–143 °C. 1H NMR (300 MHz, CDCl3): δ = 8.40 (s, 1 H),
3JH,H = 8.4 Hz, 2 H), 7.40–7.28 (m, 3 H), 7.24–7.17 (m, 2 H), 7.07 (d,
3JH,H = 15.8 Hz, 1 H), 5.62 (s, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 152.5, 147.0, 145.0, 138.7, 137.1, 136.5, 135.9, 129.2, 129.1, 128.3,
127.6, 126.8, 126.0, 122.1, 118.5, 115.3, 114.7, 45.6 ppm. MS (ES+):
m/z (%) = 458.0 (100) [M + H]+. HRMS (ESI) calcd. for C22H16N3BrF3
458.0480, found 458.0481.
3
8.15 (s, 1 H), 7.93 (d, JH,H = 15.6 Hz, 1 H), 7.38–7.26 (m, 5 H), 7.23–
3
7.14 (m, 3 H), 7.09–7.03 (m, 1 H), 6.99 (d, JH,H = 15.7 Hz, 1 H), 5.60
(s, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 161.4 (d, JF,C = 245 Hz),
Eur. J. Org. Chem. 2016, 2421–2434
2431
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim