22 in KBr pellets. 1H and 13C NMR (TMS used as internal
standard) spectra were collected in CDCl3 with a Bruker ARX
300 spectrometer. High resolution mass spectra for all the new
compounds were done by a Micromass Q-Tof instrument (ESI).
Thin layer chromatography was carried out on Silica Gel 60 F-254
TLC plates. 20 cm ¥ 20 cm Gel 60 F-254 TLC plates were used for
Isolation. Flash chromatography was performed on silica gel 60
(200–300 mesh).
7.01–7.08 (m, 1H), 6.63–6.64 (m, 1H), 6.31–6.32 (m, 1H), 4.26–
4.31 (m, 1H), 3.92 (t, J = 10.8 Hz, 1H), 3.38 (dd, J = 5.2, 11.0
Hz, 1H), 2.46 (s, 3H), 1.52 (t, J = 1.2 Hz, 3H) ppm; 13C NMR (75
MHz, CDCl3): d = 143.83, 139.11, 133.56, 132.57, 129.71, 129.41,
128.20, 128.08, 127.90, 127.24, 126.86, 123.84, 55.25, 47.77, 21.61,
12.09 ppm; IR (KBr): u = 2975, 1469 cm-1; MS (HRMS/[M +
Na]+) Calcd for C18H18ClNO2SNa: 370.0639, Found: 370.0650.
4-Methyl-3-p-tolyl-1-tosyl-2,3-dihydro-1H-pyrrole (2e)
Typical procedure for the intramolecular Heck reaction
White solid, m.p. 46–48 ◦C; 1H NMR (300 MHz, CDCl3): d = 7.69
(d, J = 8.3 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 8.0 Hz,
2H), 6.64 (d, J = 7.9 Hz, 2H), 6.23–6.24 (m, 1H), 3.92 (t, J = 10.7
Hz, 1H), 3.68–3.74 (m, 1H), 3.34 (dd, J = 6.2, 10.8 Hz, 1H), 2.49
(s, 3H), 2.28 (s, 3H), 1.43–1.41 (m, 3H) ppm; 13C NMR (75 MHz,
CDCl3): d = 143.76, 138.79, 136.64, 132.44, 129.71, 129.31, 128.02,
127.31, 125.48, 125.16, 56.10, 51.83, 21.66, 21.06, 11.92 ppm; IR
(KBr): u = 2925, 2855, 1463 cm-1; MS (HRMS/[M + Na]+) Calcd
for C19H21NO2SNa: 350.1185, Found: 350.1194.
Into a dry vial was added substrate 1 (0.5 mmol), freshly dried
K2CO3 (138 mg, 1 mmol), Pd(OAc)2 (1.1 mg, 1 mol%) and freshly
distilled DMF (1.0 mL) under a nitrogen atmosphere. The mixture
was stirred at 60 ◦C for 24 h. After cooling, the reaction was
quenched with water (10 mL). The aqueous phase was extracted
with EtOAc (3 ¥ 20 mL). The combined organic layers were
washed with brine, dried with anhydrous Na2SO4, concentrated
and purified by column (EtOAc/petroleum ether, 1 : 20 v/v) to
give the product.
4-(4-Methyl-1-tosyl-2,3-dihydro-1H-pyrrol-3-yl)phenyl acetate
(2f)
4-Methyl-3-phenyl-1-tosyl-2,3-dihydro-1H-pyrrole (2a)
◦
Colorless oil. 1H NMR (300 MHz, CDCl3): d = 7.69–7.65 (m, 2H),
7.34 (d, J = 7.7 Hz, 2H), 6.90–6.85 (m, 2H), 6.77–6.73 (m, 2H),
6.25–6.24 (t, J = 1.6 Hz, 1H), 3.91 (t, J = 10.8 Hz, 1H), 3.77–3.71
(m, 1H), 3.34 (dd, J = 6.0, 10.8 Hz, 1H), 2.46 (s, 3H), 2.27 (s,
3H), 1.42 (t, J = 1.4 Hz, 3H) ppm; 13C NMR (75 MHz, CDCl3):
d = 169.42, 149.60, 143.90, 139.29, 132.38, 129.79, 128.36, 127.98,
125.85, 124.75, 121.71, 55.96, 51.60, 21.61, 21.14, 11.94 ppm; IR
(KBr): u = 2923, 1758, 1597, 1503 cm-1; MS (HRMS/[M + Na]+)
Calcd for C20H21NO4SNa: 394.1084, Found: 394.1080.
1
White solid, m.p. 64–66 C; H NMR (300 MHz, CDCl3): d =
7.67–7.71 (m, 2H), 7.34–7.38 (m, 2H), 7.14–7.17 (m, 3H), 6.74–
6.77 (m, 2H), 6.26–6.27 (m, 1H), 3.94 (t, J = 10.7 Hz, 1H), 3.71–
3.77 (m, 1H), 3.38 (dd, J = 6.1, 10.8 Hz, 1H), 2.48 (s, 3H),
1.43 (t, J = 1.3 Hz, 3H) ppm; 13C NMR (75 MHz, CDCl3): d
= 143.52, 141.44, 131.99, 129.42, 128.24, 127.58, 126.98, 126.61,
125.26, 124.72, 55.68, 51.71, 21.17, 11.50 ppm; IR (KBr): u = 3094,
2947, 1662, 1597, 1493 cm-1; MS (HRMS/[M + Na]+) Calcd for
C18H19NO2SNa: 336.1029, Found: 336.1019.
3-(4-tert-Butylphenyl)-4-methyl-1-tosyl-2,3-dihydro-1H-pyrrole
3-(4-Chlorophenyl)-4-methyl-1-tosyl-2,3-dihydro-1H-pyrrole (2b)
(2g)
1
Colorless oil; H NMR (300 MHz, CDCl3): d = 7.67–7.69 (m,
White solid, m.p. 104–106 ◦C. 1H NMR (300 MHz, CDCl3): d =
7.73–7.68 (m, 2H), 7.36 (d, J = 7.9 Hz, 2H), 7.20–7.16 (m, 2H),
6.71–6.66 (m, 2H), 6.26–6.25 (m, 1H), 3.93 (t, J = 10.6 Hz, 1H),
3.76–3.70 (m, 1H), 3.38 (dd, J = 6.2, 10.7 Hz, 1H), 2.50 (s, 3H), 1.44
(t, J = 1.4 Hz, 3H), 1.29 (s, 9H) ppm; 13C NMR (75 MHz, CDCl3):
d = 149.85, 143.75, 138.66, 132.56, 129.77, 128.04, 127.05, 125.49,
125.46, 125.26, 56.05, 51.74, 34.41, 31.36, 21.66, 12.03 ppm; IR
(KBr): u = 2960, 2868, 1596, 1509 cm-1; MS (HRMS/[M + Na]+)
Calcd for C22H27NO2SNa: 392.1655, Found: 392.1666.
2H), 7.35 (d, J = 8.0 Hz, 2H), 7.10–7.15 (m, 2H), 6.67–6.72 (m,
2H), 6.25–6.26 (m, 1H), 3.92 (t, J = 11.0 Hz, 1H), 3.74–3.68 (m,
1H), 3.34 (dd, J = 6.0, 10.9 Hz, 1H), 2.49 (s, 3H), 1.42 (t, J = 1.2
Hz, 3H) ppm; 13C NMR (75 MHz, CDCl3): d = 143.93, 140.36,
132.82, 132.46, 129.77, 128.80, 128.72, 127.98, 126.04, 124.45,
55.88, 51.57, 21.62, 11.85 ppm; IR (KBr): u = 2921, 1489 cm-1;
MS (HRMS/[M + Na]+) Calcd for C18H18ClNO2SNa: 370.0639,
Found: 370.0629.
3-(3-Chlorophenyl)-4-methyl-1-tosyl-2,3-dihydro-1H-pyrrole (2c)
4-(4-Methyl-1-tosyl-2,3-dihydro-1H-pyrrol-3-yl)benzonitrile (2h)
White solid, m.p. 86–88 ◦C; 1H NMR (300 MHz, CDCl3): d = 7.68
(d, J = 8.3 Hz, 2H), 7.37 (d, J = 8.0 Hz, 2H), 7.07–7.17 (m, 2H),
6.70–6.72 (m, 1H), 6.61–6.62 (m, 1 H), 6.26–6.27 (m, 1H), 3.95
(t, J = 11.0 Hz, 1H), 3.73–3.69 (m, 1H), 3.33 (dd, J = 6.0, 11.0
Hz, 1H), 2.48 (s, 3H), 1.43 (t, J = 1.2 Hz, 3H) ppm; 13C NMR (75
MHz, CDCl3): d = 144.18, 144.00, 134.62, 132.14, 129.89, 129.85,
127.94, 127.35, 127.28, 126.25, 125.83, 124.17, 55.75, 51.88, 21.75,
11.92 ppm; IR (KBr): u = 2979, 1650, 1476 cm-1; MS (HRMS/[M
+ Na]+) Calcd for C18H18ClNO2SNa: 370.0639, Found: 370.0646.
White solid, m.p. 144–146 ◦C; 1H NMR (300 MHz, CDCl3): d =
7.65–7.69 (m, 2H), 7.43–7.47 (m, 2H), 7.35 (d, J = 7.8 Hz, 2H),
6.90–6.87 (m, 2H), 6.29–6.30 (m, 1H), 3.91 (t, J = 10.8 Hz, 1H),
3.75–3.80 (m, 1H), 3.35–3.40 (dd, J = 5.2, 10.9 Hz, 1H), 2.49 (s,
3H), 1.42 (t, J = 1.1 Hz, 3H) ppm; 13C NMR (75 MHz, CDCl3):
d = 147.32, 144.16, 132.54, 132.23, 129.87, 128.19, 127.98, 126.71,
123.75, 118.66, 111.04, 55.55, 52.09, 21.68, 11.93 ppm; IR (KBr):
u = 2924, 2882, 2223, 1601 cm-1; MS (HRMS/[M + Na]+) Calcd
for C19H18N2O2SNa: 361.0981, Found: 361.0973.
3-(2-Chlorophenyl)-4-methyl-1-tosyl-2,3-dihydro-1H-pyrrole (2d)
4-(4-Methyl-1-tosyl-2,5-dihydro-1H-pyrrol-3-yl)benzonitrile (3h)
White solid, m.p. 122–124 ◦C; 1H NMR (300 MHz, CDCl3): d =
7.66 (d, J = 8.3 Hz, 2H), 7.26–7.32 (m, 3H), 7.11–713 (m, 1H),
◦
1
White solid, m.p. 168–170 C; H NMR (300 MHz, CDCl3): d
= 7.78–7.73 (m, 2H), 7.64–7.60 (m, 2H), 7.33 (d, J = 7.8 Hz,
This journal is
The Royal Society of Chemistry 2011
Org. Biomol. Chem., 2011, 9, 5833–5837 | 5835
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