Paper
Organic & Biomolecular Chemistry
Synthesis of 1-benzyl 2-methyl 6-bromo-5-methoxy-1H-indole-
Synthesis of 1-tert-butyl 2-methyl 1H-pyrrolo[3,2-b]pyridine-
1,2-dicarboxylate (9)
1,2-dicarboxylate (12)
1
White solid (0.145 g, 69%); H NMR (300 MHz, CDCl3) δ: 8.34 Colorless oil (0.130 g, 94%); 1H NMR (300 MHz, CDCl3) δ:
(s, 1H, Ar), 7.47–7.39 (m, 5H, Ar), 7.03 (s, 1H, Ar), 7.02 (s, 1H, 8.61–8.59 (d, J = 6.0 Hz, 1H, Ar), 8.38–8.35 (d, J = 9.0 Hz, 1H,
Ar), 5.41 (s, 2H, –CH2(C6H5)), 3.93 (s, 3H, –CO2CH3), 3.72 Ar), 7.34–7.30 (dd, J = 7.5 Hz, 1H, Ar), 7.22 (s, 1H, Ar), 3.96
(s, 3H, –OCH3); 13C NMR δ (CDCl3): 161.93, 152.78, 150.32, (s, 3H, –CO2CH3), 1.63 (s, 9H, –C(CH3)3); 13C NMR δ (CDCl3):
134.30, 132.25, 130.94, 128.93, 128.82, 128.76, 127.49, 119.91, 162.04, 148.43, 146.63, 145.63, 133.21, 131.22, 122.63, 120.84,
115.00, 112.48, 103.28, 69.87, 56.54, 52.41; HRMS (EI) m/z: 114.26, 85.55, 52.64, 27.76; HRMS (EI) m/z: [M+] Calcd for
[M+] Calcd for C19H16NO5 417.0212; found: 417.0223.
C14H16N2O4 276.1114; found: 276.1114.
Synthesis of 1-tert-butyl 2-methyl 4-chloro-1H-pyrrolo[3,2-c]-
pyridine-1,2-dicarboxylate (13)
Synthesis of 1-benzyl 2-methyl 4-fluoro-5-methoxy-1H-indole-
1,2-dicarboxylate (10a)
Colorless oil (0.074 g, 47%); 1H NMR (300 MHz, CDCl3) δ:
8.31–8.29 (d, J = 6.0 Hz, 1H, Ar), 7.90–7.88 (d, J = 6.0 Hz, 1H,
Ar), 7.20 (s, 1H, Ar), 3.96 (s, 3H, –CO2CH3), 1.64 (s, 9H,
–C(CH3)3); 13C NMR δ (CDCl3): 161.26, 147.94, 145.41, 145.07,
142.83, 131.48, 122.82, 111.93, 109.26, 86.43, 52.73, 27.70;
HRMS (EI) m/z: [M+] Calcd for C14H15ClN2O4 310.0720; found
310.0711.
Off-white solid (0.124 g, 69%); 1H NMR (300 MHz, CDCl3) δ:
7.79–7.76 (d, J = 9.0 Hz, 1H, Ar), 7.46–4.39 (m, 5H, Ar), 7.16
(s, 1H, Ar), 7.13–7.08 (t, J = 7.5 Hz, 1H, Ar), 5.40 (s, 2H, –
CH2(C6H5)), 3.93 (s, 3H, –CO2CH3), 3.72 (s, 3H, –OCH3);
13C NMR δ (CDCl3): 161.77, 150.54, 146.35, 144.36, 142.87,
142.80, 134.30, 133.23, 133.18, 131.22, 128.91, 128.80, 128.74,
118.84, 118.18, 115.44, 110.61, 69.83, 57.87, 52.47; HRMS (EI)
m/z: [M+] Calcd for C19H16FNO5 357.1013; found: 357.1022.
Synthesis of 1-tert-butyl 2-methyl 1H-pyrrolo[2,3-c]pyridine-
1,2-dicarboxylate (14)
1
Synthesis of 1-tert-butyl 2-methyl 4-fluoro-5-methoxy-1H-
indole-1,2-dicarboxylate (10b)
Colorless oil (0.089 g, 64%); H NMR (300 MHz, CDCl3) δ: 9.42
(s, 1H, Ar), 8.47 (s, 1H, Ar), 7.54–7.52 (d, J = 6.0 Hz, 1H, Ar),
7.00 (s, 1H, Ar), 3.96 (s, 3H, –CO2CH3), 1.66 (s, 9H, –C(CH3)3);
13C NMR δ (CDCl3): 162.10, 148.23, 142.43, 137.96, 135.88,
133.38, 133.06, 111.75, 85.94, 52.80, 27.87; HRMS (EI) m/z:
[M+] Calcd for C14H16N2O4 276.1110; found 276.1099.
White solid (0.138 g, 85%); 1H NMR (300 MHz, CDCl3) δ:
7.80–7.77 (d, J = 9.0 Hz, 1H, Ar), 7.15–7.09 (m, 2H, Ar), 3.94
(s, 3H, –CO2CH3), 3.92 (s, 3H, –OCH3), 1.61 (s, 9H, –C(CH3)3);
13C NMR δ (CDCl3): 161.89, 149.07, 147.00, 143.69, 142.55,
142.44, 133.63, 133.53, 131.27, 118.20, 117.95, 115.37, 110.46,
110.40, 109.76, 84.90, 57.93, 52.44, 27.78; HRMS (EI) m/z: [M+]
Calcd for C16H18FNO5 323.1169; found: 323.1161.
Synthesis of 1-tert-butyl 2-methyl 4-bromo-1H-pyrrolo[2,3-c]-
pyridine-1,2-dicarboxylate (15)
1
White solid (0.091 g, 51%); H NMR (300 MHz, CDCl3) δ: 9.32
(s, 1H, Ar), 8.54 (s, 1H, Ar), 7.06 (s, 1H, Ar), 3.97 (s, 3H,
–CO2CH3), 1.66 (s, 9H, –C(CH3)3); 13C NMR δ (CDCl3): 161.59,
147.85, 143.25, 136.42, 133.85, 133.73, 133.49, 113.05, 111.31,
86.55, 52.91, 27.80; HRMS (EI) m/z: [M+] Calcd for
C14H15BrN2O4 354.0215; found 354.0219.
Synthesis of 1-benzyl 2-methyl 4,6-difluoro-5-methoxy-1H-
indole-1,2-dicarboxylate (11a)
White solid (0.158 g, 84%); 1H NMR (300 MHz, CDCl3) δ:
7.69–7.65 (d, J = 12.0 Hz, 1H, Ar), 7.47–7.37 (m, 5H, Ar), 7.16
(s, 1H, Ar), 5.40 (s, 2H, –CH2(C6H5)), 4.00 (s, 3H, –CO2CH3),
3.72 (s, 3H, –OCH3); 13C NMR δ (CDCl3): 161.34, 157.75,
150.24, 134.05, 130.67, 130.61, 129.03, 128.88, 128.77, 113.78,
110.84, 110.82, 99.46, 99.40, 99.10, 99.04, 70.12, 62.39, 52.47;
HRMS (EI) m/z: [M+] Calcd for C19H15F2NO5 375.0918; found:
375.0891.
Synthesis of 1-benzyl 2-methyl 5-chloro-1H-pyrrolo[2,3-c]-
pyridine-1,2-dicarboxylate (16a)
1
White solid (0.154 g, 89%); H NMR (300 MHz, CDCl3) δ: 9.12
(s, 1H, Ar), 7.53 (s, 1H, Ar), 7.48–7.39 (m, 5H, Ar), 6.94 (s, 1H,
Ar), 5.45 (s, 2H, –CH2(C6H5)), 3.77 (s, 3H, –CO2CH3); 13C NMR
δ (CDCl3): 161.46, 149.35, 144.36, 137.31, 136.39, 135.00,
133.61, 132.43, 129.29, 129.05, 128.93, 128.91, 115.92, 111.24,
70.65, 52.93; HRMS (EI) m/z: [M+] Calcd for C17H13ClN2O4
344.0564; found 344.0558.
Synthesis of 1-tert-butyl 2-methyl 4,6-difluoro-5-methoxy-1H-
indole-1,2-dicarboxylate (11b)
Colorless oil (0.149 g, 87%); 1H NMR (300 MHz, CDCl3) δ:
7.70–7.66 (d, J = 12.0 Hz, 1H, Ar), 7.13 (s, 1H, Ar), 4.00 (s, 3H,
–CO2CH3), 3.92 (s, 3H, –OCH3), 1.62 (s, 9H, –C(CH3)3);
13C NMR δ (CDCl3): 161.48, 157.70, 157.63, 154.42, 154.36,
Synthesis of 1-tert-butyl 2-methyl 5-chloro-1H-pyrrolo[2,3-c]-
pyridine-1,2-dicarboxylate (16b)
150.29, 150.19, 148.74, 146.95, 146.86, 132.74, 130.71, 130.66, Yellow oil (0.147 g, 94%); 1H NMR (300 MHz, CDCl3) δ: 9.17
113.85, 113.83, 113.58, 113.56, 110.04, 110.01, 99.18, 99.12, (s, 1H, Ar), 7.54 (s, 1H, Ar), 6.92 (s, 1H, Ar), 3.97 (s, 3H,
98.82, 98.76, 85.48, 62.39, 52.46, 27.72; HRMS (EI) m/z: [M+] –CO2CH3), 1.65 (s, 9H, –C(CH3)3); 13C NMR δ (CDCl3): 161.64,
Calcd for C16H17F2NO5 341.1075; found: 341.1067.
147.83, 143.88, 137.21, 136.15, 135.05, 132.62, 115.76,
5136 | Org. Biomol. Chem., 2015, 13, 5131–5138
This journal is © The Royal Society of Chemistry 2015