Job/Unit: O50166
/KAP1
Date: 25-03-15 17:16:28
Pages: 8
Synthesis of Polysubstituted Pyrroles
(s, 3 H), 3.70 (s, 3 H), 2.56 (q, J = 7.5 Hz, 2 H), 2.01 (dt, J = 13.9,
7.0 Hz, 1 H), 0.96 (t, J = 7.5 Hz, 3 H), 0.87 (d, J = 6.7 Hz, 6
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 167.0, 161.5, 141.0,
138.7, 128.2, 128.2, 125.7, 122.4, 120.5, 118.6, 51.9, 51.7, 51.6, 30.5,
34.4, 19.8, 17.8, 14.0 ppm. HRMS (ESI): m/z calcd. for C21H28NO4
[M + H]+ 358.2018; found 358.2011.
= 165.8, 125.0, 121.4, 119.0, 113.4, 60.6, 50.5, 33.6, 23.9, 11.7 ppm.
HRMS (ESI): m/z calcd. for C12H18NO2 [M + H]+ 208.1338; found
208.1342.
Methyl 1-Cyclohexyl-4-methyl-1H-pyrrole-3-carboxylate (3bi): 1H
NMR (500 MHz, CDCl3): δ = 7.31 (d, J = 2.5 Hz, 1 H), 6.46 (dd,
J = 2.2, 0.9 Hz, 1 H), 3.78 (s, 3 H), 3.75–3.66 (m, 1 H), 2.26 (d, J
= 0.9 Hz, 3 H), 2.10–2.03 (m, 2 H), 1.92–1.85 (m, 2 H), 1.76–1.71
(m, 1 H), 1.59 (qd, J = 12.5, 3.4 Hz, 2 H), 1.43–1.34 (m, 2 H), 1.23
(ddd, J = 12.8, 8.3, 3.6 Hz, 1 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 165.8, 124.4, 121.0, 118.5, 113.3, 59.0, 50.5, 34.3, 25.5,
25.3, 11.7 ppm. HRMS (ESI): m/z calcd. for C13H20NO2 [M +
H]+ 222.1494; found 222.1492.
Methyl 1-Benzyl-4-methyl-1H-pyrrole-3-carboxylate (3ba): 1H
NMR (500 MHz, CDCl3): δ = 7.38–7.30 (m, 3 H), 7.28 (d, J =
2.4 Hz, 1 H), 7.16 (d, J = 6.9 Hz, 2 H), 6.42 (d, J = 1.2 Hz, 1 H),
4.99 (s, 2 H), 3.79 (s, 3 H), 2.27 (d, J = 0.8 Hz, 3 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 165.7, 136.8, 128.9, 128.0, 127.3,
127.0, 122.0, 120.7, 114.3, 53.7, 50.6, 11.7 ppm. HRMS (ESI): m/z
calcd. for C14H16NO2 [M + H]+ 230.1181; found 230.1184.
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Methyl 4-Methyl-1-octyl-1H-pyrrole-3-carboxylate (3bj): H NMR
Methyl 4-Methyl-1-propyl-1H-pyrrole-3-carboxylate (3bb): 1H
NMR (500 MHz, CDCl3): δ = 7.22 (d, J = 2.4 Hz, 1 H), 6.40–6.36
(m, 1 H), 3.78 (s, 3 H), 3.75 (t, J = 7.0 Hz, 2 H), 2.26 (d, J =
0.7 Hz, 3 H), 1.77 (m, 2 H), 0.90 (t, J = 7.4 Hz, 3 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 165.8, 126.6, 121.5, 120.3, 113.6,
51.6, 50.6, 24.4, 11.7, 11.2 ppm. HRMS (ESI): m/z calcd. for
C10H16NO2 [M + H]+ 182.1181; found 182.1186.
(500 MHz, CDCl3): δ = 7.22 (d, J = 2.4 Hz, 1 H), 6.38 (dd, J =
2.3, 1.0 Hz, 1 H), 3.81–3.76 (m, 5 H), 2.26 (d, J = 1.0 Hz, 3 H),
1.73 (dd, J = 14.1, 7.2 Hz, 2 H), 1.31–1.24 (m, 10 H), 0.89 (t, J =
7.0 Hz, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 165.8, 126.5,
121.5, 120.2, 113.6, 50.5, 49.9, 31.7, 31.1, 29.1, 26.6, 22.59, 14.0,
11.7 ppm. HRMS (ESI): m/z calcd. for C15H26NO2 [M + H]+
252.1964; found 252.1967.
Methyl 1-Isopropyl-4-methyl-1H-pyrrole-3-carboxylate (3bc): 1H
NMR (500 MHz, CDCl3): δ = 7.30 (d, J = 2.5 Hz, 1 H), 6.46 (d,
J = 1.3 Hz, 1 H), 4.16 (dt, J = 13.4, 6.7 Hz, 1 H), 3.79 (s, 3 H),
2.27 (d, J = 0.7 Hz, 3 H), 1.43 (d, J = 6.7 Hz, 6 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 165.8, 124.2, 121.3, 118.2, 113.4, 51.2, 50.5,
23.6, 11.7 ppm. HRMS (ESI): m/z calcd. for C10H16NO2 [M +
H]+ 182.1181; found 182.1180.
Methyl 4-Benzyl-1-butyl-5-methyl-1H-pyrrole-3-carboxylate (3bk):
1H NMR (500 MHz, CDCl3): δ = 7.27–7.23 (m, 3 H), 7.20 (d, J =
6.9 Hz, 2 H), 7.15 (t, J = 7.2 Hz, 1 H), 4.13 (s, 2 H), 3.81 (t, J =
7.3 Hz, 2 H), 3.74 (s, 3 H), 2.16 (s, 3 H), 1.75–1.68 (m, 2 H), 1.42–
1.33 (m, 2 H), 0.98 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 165.6, 142.4, 128.2, 128.1, 127.2, 125.7, 125.3, 119.9,
112.5, 50.5, 47.1, 33.0, 30.6, 19.9, 13.7, 9.7 ppm. HRMS (ESI): m/z
calcd. for C18H24NO2 [M + H]+ 286.1807; found 286.1815.
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Methyl 1-Butyl-4-methyl-1H-pyrrole-3-carboxylate (3bd): H NMR
Methyl 4-Benzyl-5-ethyl-1-isobutyl-1H-pyrrole-3-carboxylate (3bm):
1H NMR (500 MHz, CDCl3): δ = 7.27–7.22 (m, 3 H), 7.22–7.17
(m, 2 H), 7.14 (t, J = 7.2 Hz, 1 H), 4.15 (s, 2 H), 3.72 (s, 3 H), 3.63
(d, J = 7.6 Hz, 2 H), 2.56 (q, J = 7.5 Hz, 2 H), 2.10–2.02 (m, 1 H),
1.02 (t, J = 7.5 Hz, 3 H), 0.96 (s, 3 H), 0.94 (s, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 165.6, 142.6, 133.7, 128.1, 128.0, 126.2,
125.3, 119.1, 112.7, 54.6, 50.5, 30.5, 30.1, 20.1, 17.3, 14.7 ppm.
HRMS (ESI): m/z calcd. for C19H26NO2 [M + H]+ 300.1964; found
300.1961.
(500 MHz, CDCl3): δ = 7.22 (d, J = 2.5 Hz, 1 H), 6.38 (dd, J =
2.3, 1.0 Hz, 1 H), 3.81–3.78 (m, 5 H), 2.26 (d, J = 1.0 Hz, 3 H),
1.76–1.70 (m, 2 H), 1.35–1.27 (m, 2 H), 0.95–0.91 (m, 3 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 165.8, 126.5, 121.5, 120.2, 113.6,
50.5, 49.6, 33.1, 19.8, 13.5, 11.7 ppm. HRMS (ESI): m/z calcd. for
C11H18NO2 [M + H]+ 196.1338; found 196.1329.
Methyl 1-Isobutyl-4-methyl-1H-pyrrole-3-carboxylate (3be): 1H
NMR (500 MHz, CDCl3): δ = 7.19 (d, J = 2.4 Hz, 1 H), 6.36 (dd,
J = 2.3, 1.0 Hz, 1 H), 3.79 (s, 3 H), 3.58 (d, J = 7.3 Hz, 2 H), 2.26
(d, J = 1.0 Hz, 3 H), 2.00 (dt, J = 13.6, 6.9 Hz, 1 H), 0.91–0.89 (m,
6 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 165.8, 127.0, 121.4,
120.7, 113.6, 57.7, 50.5, 30.2, 19.9, 11.7 ppm. HRMS (ESI): m/z
calcd. for C11H18NO2 [M + H]+ 196.1338; found 196.1348.
Methyl
4-Benzyl-1-sec-butyl-5-propyl-1H-pyrrole-3-carboxylate
1
(3bn): H NMR (500 MHz, CDCl3): δ = 7.33 (s, 1 H), 7.23 (t, J =
7.5 Hz, 2 H), 7.18–7.11 (m, 3 H), 4.13 (s, 2 H), 3.99 (dd, J = 13.8,
6.9 Hz, 1 H), 3.71 (s, 3 H), 2.51 (td, J = 8.4, 2.6 Hz, 2 H), 1.78 (m,
2 H), 1.43 (d, J = 6.7 Hz, 3 H), 1.38 (ddd, J = 14.9, 10.2, 4.1 Hz,
2 H), 0.90 (t, J = 7.3 Hz, 3 H), 0.85 (t, J = 7.4 Hz, 3 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 165.6, 142.6, 132.3, 128.1, 128.0,
125.2, 121.8, 118.8, 113.3, 53.0, 50.4, 31.1, 30.5, 26.2, 23.6, 22.3,
13.9, 10.9 ppm. HRMS (ESI): m/z calcd. for C20H28NO2 [M +
H]+ 314.2120; found 314.2117.
Methyl 1-sec-Butyl-4-methyl-1H-pyrrole-3-carboxylate (3bf): 1H
NMR (500 MHz, CDCl3): δ = 7.27 (d, J = 4.9 Hz, 1 H), 6.43 (d,
J = 1.2 Hz, 1 H), 3.85 (dt, J = 13.8, 6.9 Hz, 1 H), 3.79 (s, 3 H),
2.27 (d, J = 0.7 Hz, 3 H), 1.75–1.69 (m, 2 H), 1.42 (d, J = 6.8 Hz,
3 H), 0.82 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR (125 MHz, CDCl3):
δ = 165.9, 124.8, 121.2, 118.3, 113.3, 57.6, 50.5, 30.8, 21.7, 11.8,
10.7 ppm. HRMS (ESI): m/z calcd. for C11H18NO2 [M + H]+
196.1338; found 196.1337.
Methyl
4-Benzyl-1-butyl-2,5-dimethyl-1H-pyrrole-3-carboxylate
1
(3ck): H NMR (500 MHz, CDCl3): δ = 7.25 (d, J = 7.5 Hz, 2 H),
7.15 (dd, J = 15.5, 7.4 Hz, 3 H), 4.10 (s, 2 H), 3.84–3.78 (m, 2 H),
3.71 (s, 3 H), 2.56 (s, 3 H), 2.20 (s, 3 H), 1.64 (tt, J = 7.8, 6.8 Hz,
2 H), 1.46–1.37 (m, 2 H), 1.01 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 166.5, 142.7, 134.7, 128.0, 127.9, 125.2,
125.1, 118.5, 109.7, 50.0, 43.4, 32.7, 31.1, 20.0, 13.7, 11.6, 9.8 ppm.
HRMS (ESI): m/z calcd. for C19H26NO2 [M + H]+ 300.1964; found
300.1967.
Methyl 1-tert-Butyl-4-methyl-1H-pyrrole-3-carboxylate (3bg): 1H
NMR (500 MHz, CDCl3): δ = 7.40 (d, J = 2.6 Hz, 1 H), 6.58 (d,
J = 1.5 Hz, 1 H), 3.80 (s, 3 H), 2.28 (s, 3 H), 1.52 (s, 9 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 166.0, 123.8, 121.1, 117.5, 113.2,
55.3, 50.6, 30.5, 11.8 ppm. HRMS (ESI): m/z calcd. for C11H18NO2
[M + H]+ 196.1338; found 196.1347.
Methyl 1-Cyclopentyl-4-methyl-1H-pyrrole-3-carboxylate (3bh): 1H Methyl
1-Butyl-2,4-dimethyl-5-phenyl-1H-pyrrole-3-carboxylate
NMR (500 MHz, CDCl3): δ = 7.30 (d, J = 2.5 Hz, 1 H), 6.46 (dd, (3co): 1H NMR (500 MHz, CDCl3): δ = 7.43 (dd, J = 10.1, 4.5 Hz,
J = 2.3, 1.0 Hz, 1 H), 4.34–4.27 (m, 1 H), 3.79 (s, 3 H), 2.26 (d, J
= 0.9 Hz, 3 H), 2.14 (dddd, J = 9.5, 5.7, 4.3, 2.5 Hz, 2 H), 1.87–1.79
2 H), 7.40–7.34 (m, 1 H), 7.26 (d, J = 6.8 Hz, 2 H), 3.83 (s, 3 H),
3.75–3.69 (m, 2 H), 2.58 (s, 3 H), 2.11 (s, 3 H), 1.43 (ddd, J = 12.7,
(m, 4 H), 1.73–1.67 (m, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ 10.5, 6.8 Hz, 2 H), 1.16–1.07 (m, 2 H), 0.75 (t, J = 7.4 Hz, 3
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