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(100 g) that was combined with concentrated HCl (5 mL). The result- The yellow solution was then poured over crushed ice (100 g), and
ing mixture was extracted with CHCl3 (2 × 25 mL). The combined
organic layers were then washed with brine and dried with Na2SO4.
the mixture was acidified with concentrated HCl (5 mL). The solid
was removed by filtration and dried to give the crude product,
The solvent was removed in vacuo to give the crude phosphonate which was crystallized (MeOH) to afford divinyl indole 10b (1.81 g,
ester 7 (2.00 g, 91 %) as a thick brown liquid. 1H NMR (300 MHz,
CDCl3): δ = 7.95–7.92 (m, 3 H), 7.86 (d, J = 2.4 Hz, 1 H), 7.66–7.59
(m, 4 H), 7.53–7.48 (m, 2 H), 7.40–7.35 (m, 1 H), 7.30–7.25 (m, 2 H),
78 %) as a yellow solid; m.p. 136–138 °C. 1H NMR (300 MHz, CDCl3):
δ = 8.25 (d, J = 8.1 Hz, 1 H), 7.78–7.76 (m, 4 H), 7.56 (d, J = 16.2 Hz,
1 H), 7.43–7.15 (m, 9 H), 6.53 (d, J = 16.2 Hz, 1 H), 6.46 (d, J =
7.20–7.11 (m, 1 H), 7.06–6.96 (m, 2 H), 4.11–3.33 (m, 8 H), 1.29–1.14 16.2 Hz, 1 H), 4.16 (q, J = 7.05 Hz, 2 H), 2.33 (s, 3 H), 1.22 (t, J =
(m, 6 H), 0.53 (m, 3 H) ppm.
7.2 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 167.2, 141.0, 139.5,
139.2, 138.0, 136.9, 136.7, 134.0, 133.6, 129.6, 129.0, 128.0, 127.1,
126.8, 125.7, 124.7, 120.5, 119.3, 117.4, 116.5, 115.3, 60.4, 21.4,
14.3 ppm. DEPT-135 (75 MHz, CDCl3): δ = 139.5, 136.7, 134.0, 129.6,
129.0, 127.1, 126.8, 125.7, 124.7, 120.5, 119.3, 116.5, 115.3, 60.4, 21.4,
14.3 ppm.
Ethyl
4-[2-(4-Methoxystyryl)-1-phenylsulfonyl-indol-3-yl]-1-
phenylsulfonyl-pyrrole-3-carboxylate (8): To a suspension of hex-
ane washed sodium hydride (175 mg, 3.65 mmol) in dry THF
(10 mL) at –10 °C under N2 was slowly added phosphonate ester 7
(1 g, 1.46 mmol) in dry THF (25 mL), and the resulting mixture was
stirred for 1 h. Then, a solution of p-anisaldehyde (0.22 g,
1.60 mmol) in dry THF (5 mL) was added, and the stirring was
continued for an additional 2 h. The yellow solution was then
poured over crushed ice (50 g), and the mixture was then acidified
with concentrated HCl (3 mL). The solid was removed by filtration
and dried to give the crude product, which was crystallized (MeOH)
to give 2-p-anisylvinylindole 8 (0.59 g, 60 %) as a colorless solid;
Ethyl 4-[2(E)-(4-Methoxystyryl)-1-phenylsulfonyl-1H-indol-3-yl]-
1H-pyrrole-3-carboxylate (11a): To
a suspension of tBuOK
(350 mg, 3.07 mmol) in dry DMF (8 mL) at 0 °C under N2 was added
TOSMIC (0.44 g, 2.25 mmol) in dry DMF (5 mL). The reaction mixture
was stirred for 15 min at the same temperature and then treated
dropwise with a solution of divinyl compound 10a (1 g, 2.05 mmol)
in dry DMF (10 mL). After the starting material was consumed (mon-
itored by TLC), the reaction mixture was quenched with crushed ice
(50 g), and the resulting mixture was extracted with CHCl3
(2 × 20 mL). The combine organic layers were dried with Na2SO4,
and the solvent was removed. The crude residue was purified by
column chromatography [hexane/ethyl acetate (EA), 9:1] to afford
pyrrole compound 11a (0.87 g, 80 %) as a yellow solid; m.p. 220–
223 °C. 1H NMR (300 MHz, CDCl3): δ = 8.64 (s, 1 H), 8.17 (d, J =
8.1 Hz, 1 H), 7.69 (d, J = 7.5 Hz, 2 H), 7.45 (d, J = 16.2 Hz, 1 H), 7.40–
7.35 (m, 2 H), 7.27–7.19 (m, 5 H), 7.10–7.08 (m, 2 H), 6.77 (d, J =
8.4 Hz, 2 H), 6.56 (s, 1 H), 6.39 (d, J = 16.2 Hz, 1 H), 3.81–3.70 (m, 5
H), 0.51 (t, J = 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
164.6, 159.6, 138.6, 136.2, 135.7, 134.2, 133.4, 132.8, 130.1, 128.8,
127.9, 126.9, 125.0, 124.6, 123.8, 120.3, 119.1, 117.4, 116.3, 116.2,
116.0, 115.1, 114.1, 59.4, 55.4, 13.5 ppm. DEPT-135 (75 MHz, CDCl3):
δ = 138.6, 138.5, 133.8, 132.5, 131.4, 130.0, 129.3, 128.6, 125.2, 124.4,
121.0, 119.6, 118.9, 63.6, 60.1, 18.6 ppm. C30H26N2O5S (526.61):
calcd. C 68.42, H 4.98, N 5.32; found C 68.63, H 4.71, N 5.41.
1
m.p. 170–172 °C. H NMR (300 MHz, CDCl3): δ = 8.24 (d, J = 8.4 Hz,
1 H), 7.89 (d, J = 2.1 Hz, 1 H), 7.84 (d, J = 7.8 Hz, 2 H), 7.73 (d, J =
7.8 Hz, 2 H), 7.57 (t, J = 7.2 Hz, 1 H), 7.49–7.26 (m, 7 H), 7.20–7.06
(m, 5 H), 6.83 (d, J = 8.4 Hz, 2 H), 6.23 (d, J = 16.2 Hz, 1 H), 3.92–
3.80 (m, 5 H), 0.67 (t, J = 7.2 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 162.8, 159.8, 138.5, 138.0, 136.3, 136.1, 134.8, 134.4, 133.6, 131.6,
129.7, 129.5, 128.9, 127.9, 126.9, 126.8, 126.6, 125.0, 124.0, 121.0,
120.7, 120.2, 119.8, 115.9, 115.1, 114.6, 114.1, 60.2, 55.4, 13.5 ppm.
DEPT-135 (75 MHz, CDCl3): δ = 134.8, 134.4, 133.6, 129.6, 128.9,
127.9, 126.9, 126.8, 126.6, 125.0, 124.0, 121.0, 119.8, 115.9, 115.1,
114.1, 60.2, 55.4, 13.5 ppm. C36H30N2O7S2 (666.76): calcd. C 64.85,
H 4.54, N 4.20; found C 65.05, H 4.68, N 4.32.
Ethyl (E)-3-[2(E)-(4-Methoxystyryl)-1-(phenylsulfonyl)-1H-indol-
3-yl]acrylate (10a): To a suspension of hexane washed sodium
hydride (710 mg, 14.83 mmol) in dry THF (20 mL) at –10 °C under
N2, was slowly added (E)-ethyl 3-{2-[(diethoxyphosphoryl)methyl]-1-
(phenylsulfonyl)1H-indol-3-yl}acrylate (9,[14] 3 g, 5.93 mmol) in dry
THF (40 mL), and the resulting mixture was stirred for 1 h. Then, a
solution of p-anisaldehyde (0.89 g, 6.52 mmol) in dry THF (8 mL)
was added, and the stirring was continued for an additional 2 h.
The yellow solution was then poured over crushed ice (100 g), and
the mixture was acidified with concentrated HCl (5 mL). The solid
was removed by filtration and dried to give the crude product,
which was crystallized (MeOH) to give divinyl indole 10a (2.35 g,
80 %) as a yellow solid; m.p. 140–142 °C. 1H NMR (300 MHz, CDCl3):
δ = 8.33 (d, J = 7.8 Hz, 1 H), 7.86–7.68 (m, 4 H), 7.57–7.29 (m, 8 H),
6.96 (d, J = 8.4 Hz, 2 H), 6.62–6.51 (m, 2 H), 4.17 (q, J = 7.2 Hz, 2 H),
3.80 (s, 3 H), 1.23 (t, J = 7.2 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 167.3, 160.5, 141.3, 139.2, 138.1, 136.9, 136.8, 134.0, 129.2, 129.1,
128.6, 128.1, 126.9, 125.6, 124.7, 120.5, 119.1, 117.2, 115.3, 115.2,
114.4, 60.4, 55.4, 14.4 ppm. DEPT-135 (75 MHz, CDCl3): δ = 139.2,
136.8, 134.0, 129.1, 128.7, 126.9, 125.6, 124.7, 120.5, 119.1, 115.3,
114.3, 60.4, 55.4, 14.4 ppm.
Ethyl 4-[2(E)-(4-Methylstyryl)-1-(phenylsulfonyl)-1H-indol-3-yl]-
1H-pyrrole-3-carboxylate (11b): To
a suspension of tBuOK
(360 mg, 3.18 mmol) in dry DMF (8 mL) at 0 °C under N2 was added
TOSMIC (0.45 g, 2.33 mmol) in dry DMF (5 mL). The reaction mixture
was stirred for 15 min at the same temperature and then treated
dropwise with a solution of divinyl indole 10b (1 g, 2.12 mmol) in
dry DMF (8 mL). After the starting material was consumed (moni-
tored by TLC), a similar workup procedure as that of 2-p-anisylvinyl-
indole 11a was followed to afford 2-p-tolylvinylindole 11b (0.81 g,
75 %) as a yellow solid; m.p. 230–232 °C. 1H NMR (300 MHz, CDCl3):
δ = 11.61 (s, 1 H), 8.54 (d, J = 6.9 Hz, 1 H), 8.12 (d, J = 7.8 Hz, 2 H),
7.89–7.74 (m, 5 H), 7.65–7.49 (m, 7 H), 7.06 (s, 1 H), 6.90 (d, J =
16.2 Hz, 1 H), 4.21 (q, J = 7.8 Hz, 2 H), 2.71 (s, 3 H), 1.10 (t, J =
6.6 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 169.1, 143.0, 142.5,
140.8, 139.9, 139.2, 138.8, 138.5, 137.5, 134.1, 133.8, 131.4, 131.2,
130.1, 129.4, 128.6, 125.2, 124.4, 123.1, 122.1, 119.6, 119.5, 63.6, 26.0,
18.5 ppm. DEPT-135 (75 MHz, CDCl3): δ = 138.8, 138.5, 134.1, 133.8,
131.4, 131.1, 130.1, 129.4, 128.6, 125.2, 124.4, 122.1, 119.5, 63.6, 26.0,
18.5 ppm. C30H26N2O4S (510.61): calcd. C 70.57, H 5.13, N 5.49;
found C 70.71, H 5.22, N 5.28.
Ethyl (E)-3-[2(E)-(4-Methylstyryl)-1-(phenylsulfonyl)-1H-indol-3-
yl]acrylate (10b): To a suspension of hexane washed sodium
hydride (470 mg, 9.89 mmol) in dry THF (10 mL) at –10 °C under
N2 was slowly added (E)-ethyl 3-{2-[(diethoxyphosphoryl)methyl]-1-
(phenylsulfonyl)-1H-indol-3-yl}acrylate (9,[14] 2.5 g, 4.94 mmol) in
dry THF (30 mL), and the resulting mixture was stirred for 1 h. Then,
a solution of p-anisaldehyde (0.65 g, 5.43 mmol) in dry THF (5 mL)
was added, and the stirring was continued for an additional 2 h.
Ethyl 4-(4-Methoxyphenyl)-3,6-bis(phenylsulfonyl)-3,6-dihydro-
pyrrolo[2,3-c]carbazole-1-carboxylate (12)
Method 1: To a solution of 2-p-anisylvinylindole 8 (0.20 g,
0.30 mmol) in dry DCM (10 mL) at 0 °C was added anhydrous FeCl3
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