2235
G. A. Rao, M. Periasamy
Letter
Synlett
93.763(9)°, β = 96.324(10)°, γ = 99.219(11)°, v = 1808.2(4) Å3, Z =
4, ρc = 1.287 mgm−3, μ = 0.083 mm–1, T = 293(2) K. Of the 12687
J = 7.4 Hz, 1 H), 5.03 (d, J = 7.6 Hz, 1 H), 3.70–3.81 (m, 2 H), 3.42–
3.55 (m, 2 H), 2.95–3.01 (m, 1 H), 2.70–2.77 (m, 1 H), 2.40 (s, 3
H), 2.39 (s, 3 H), 1.89–2.11 (m, 6 H). 13C NMR (100 MHz, CDCl3):
δ = 150.6, 145.7, 131.9, 131.2, 130.5, 127.0, 126.8, 126.5, 125.8,
121.8, 120.0, 118.5, 62.0, 58.9, 52.5, 51.5, 41.4, 29.6, 25.0, 24.1,
22.1, 19.6. HRMS: m/z [M + H]+ calcd for C22H26N2: 319.2175;
found: 319.2174.
reflections collected, 7375 reflections were unique (Rint
=
0.0459). Refinement on all data converged at R1 = 0.1669, wR2 =
0.1900 (CCDC deposition number: 1054950).
(9) Ochowski, J.; Peczynska-Czoch, W.; Pi-tka-Ottlik, M.;
Wojtowicz-Mlochowska, H. Open Catal. J. 2011, 4, 54.
(10) (a) Kerr, G. H.; Meth-Cohn, O.; Mullock, E. B.; Suschitzky, H. J.
Chem. Soc., Perkin Trans. 1 1974, 1614. (b) Swan, G. A.; Wilcock,
J. D. J. Chem. Soc., Perkin Trans. 1 1974, 885.
(11) Minakata, S.; Ohshima, Y.; Takemiya, A.; Ryu, I.; Komatsu, M.;
Ohshiro, Y. Chem. Lett. 1997, 26, 311.
(12) (a) Kundu, D.; Bhadra, S.; Mukherjee, N.; Sreedhar, B.; Ranu, B.
C. Chem. Eur. J. 2013, 19, 15759. (b) Yong, F.-F.; Teo, Y.-C.; Chua,
G.-L.; Lim, G.-S.; Lin, Y. Tetrahedron Lett. 2011, 52, 1169. (c) Ma,
F.; Xie, X.; Zhang, L.; Peng, Z.; Ding, L.; Zhang, Z. J. Org. Chem.
2012, 77, 5279. (d) Chen, Y.-J.; Chen, H.-H. Org. Lett. 2006, 8,
5609.
(13) (a) Girard, S. A.; Knauber, T.; Li, C.-J. Angew. Chem. Int. Ed. 2014,
53, 74. (b) Li, Z.; Li, C.-J. J. Am. Chem. Soc. 2005, 127, 3672.
(c) Hari, D. P.; König, B. Org. Lett. 2011, 13, 3852.
(14) General Experimental Procedure for the Preparation of N-
Aryl-Substituted Pyrrolydines 1: To a stirred solution of K2CO3
(5.52 g, 40 mmol), KI (0.17 g, 5 mol%) in MeCN (30 mL) under
nitrogen atmosphere, 1,4-dibromobutane (2.39 mL, 20 mmol)
and aryl amines (25 mmol) were added. The reaction mixture
was refluxed for 8 h. After completion of the reaction, the
solvent was evaporated and EtOAc (50 mL) and H2O (30 mL)
were added. The organic layer was separated and extracted
with EtOAc (20 mL). The combined organic layer was washed
with brine (50 mL), dried over Na2SO4, filtered and concen-
trated. The residue was purified by column chromatography on
silica gel (100–200 mesh) using hexane as eluent to isolate the
N-aryl-substituted pyrrolidines 1 in 82–89% yields.
10-Methyl-1-(p-tolyl)-2,3,3a,3b,4,5,6,11b-octahydro-1H-
dipyrrolo[1,2-a:3′,2′-c]quinoline (2c): colorless oil; yield: 0.10
g, 62%. IR (neat): 3063, 3014, 2964, 2866, 1600, 1496, 1430,
1293, 1096, 756, 712 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.09
(d, J = 8.0 Hz, 2 H), 7.03 (d, J = 8.0 Hz, 1 H), 6.99 (s, 1 H), 6.65 (d, J
= 8.0 Hz, 3 H), 4.41 (d, J = 8.0 Hz, 1 H), 3.69 (t, J = 8.0 Hz, 1 H),
3.49 (t, J = 8.0 Hz, 1 H), 3.29–3.36 (m, 1 H), 2.72–2.87 (m, 2 H),
2.38–2.44 (m, 1 H), 2.32 (s, 3 H), 2.12–2.25 (m, 6 H), 1.98–2.04
(m, 1 H), 1.73–1.86 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ =
147.5, 145.0, 129.6, 128.8, 128.3, 127.6, 127.5, 125.6, 112.8,
112.0, 65.1, 60.1, 49.7, 48.3, 47.6, 31.9, 30.6, 22.3, 20.9, 20.3.
HRMS: m/z [M + H]+ calcd for C22H26N2: 319.2175; found:
319.2174.
1-(2,4-Dimethylphenyl)-8,10-dimethyl-2,3,3a,3b,4,5,6,11b-
octahydro-1H-dipyrrolo[1,2-a:3′,2′-c]quinoline (2d): color-
less oil; yield: 0.10 g, 59%. IR (neat): 2953, 2915, 2866, 1605,
1496, 1474, 1342, 1288, 866, 816 cm–1 1H NMR (400 MHz,
.
CDCl3): δ = 7.06 (s, 1 H), 7.00 (d, J = 8.0 Hz, 1 H), 6.92 (d, J = 8.0
Hz, 1 H), 6.77 (s, 1 H), 6.72 (s, 1 H), 4.85 (d, J = 7.6 Hz, 1 H), 3.75–
3.79 (m, 1 H), 3.66–3.72 (m, 1 H), 3.40–3.44 (m, 2 H), 2.87–2.93
(m, 1 H), 2.64–2.69 (m, 1 H), 2.34 (s, 9 H), 2.17–2.23 (m, 1 H),
2.10 (s, 3 H), 1.95–2.06 (m, 3 H), 1.84–1.92 (m, 2 H). 13C NMR
(100 MHz, CDCl3): δ = 149.0, 143.1, 132.7, 131.8, 131.6, 131.2,
127.8, 127.7, 127.4, 127.1, 125.7, 120.6, 62.9, 58.8, 52.7, 52.5,
41.6, 29.7, 25.7, 24.1, 21.8, 20.7, 20.4, 19.2. HRMS: m/z [M + H]+
calcd for C24H30N2: 347.2488; found: 347.2483.
3-(Naphthalen-1-yl)-2,3,3a,11,12,13,13a,13b-octahydro-1H-
benzo[h]dipyrrolo[1,2-a:3′,2′-c]quinoline (2e): white solid;
yield: 0.15 g, 78%; mp 203–205 °C. IR (KBr): 3036, 2953, 2926,
General Experimental Procedure for the Preparation of Tet-
racyclic Amines 2a–f: A mixture of 1 (1 mmol), T-HYDRO (0.55
mL, 4 mmol), NaOAc∙3H2O (0.54 g, 4 mmol) in cyclohexane (2
mL) was stirred for 24 h at 70 °C. After completion of the reac-
tion, the solvent was evaporated and EtOAc (10 mL) and H2O (5
mL) were added. The combined organic layer was washed with
brine (10 mL), dried over Na2SO4, filtered and concentrated. The
residue was purified by column chromatography on silica gel
(100–200 mesh) using EtOAc–hexane (1:5) as eluent to get tet-
racyclic amines.
1-Phenyl-2,3,3a,3b,4,5,6,11b-octahydro-1H-dipyrrolo[1,2-
a:3′,2′-c]quinoline (2a): white solid; yield: 0.11 g, 72%; mp
154–156 °C. IR (KBr): 3047, 2970, 2838, 2805, 1611, 1501, 1479,
1358, 740 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.29–7.38 (m, 3
H), 7.13–7.16 (m, 1 H), 6.85–6.87 (m, 2 H), 6.72–6.77 (m, 1 H),
6.54–6.59 (m, 1 H), 6.43–6.46 (m, 1 H), 5.16 (d, J = 6.4 Hz, 1 H),
3.77–3.79 (m, 1 H), 3.51–3.55 (m, 1 H), 3.29–3.44 (m, 3 H),
2.52–2.59 (m, 1 H), 2.14–2.20 (m, 1 H), 1.95–2.13 (m, 3 H),
1.84–1.92 (m, 1 H), 1.69–1.79 (m, 1 H). 13C NMR (100 MHz,
CDCl3): δ = 148.9, 143.2, 129.4, 128.8, 128.1, 123.0, 115.8, 115.5,
111.3, 110.3, 57.5, 56.6, 47.4, 46.6, 40.1, 30.3, 23.4, 23.3. HRMS:
m/z [M + H]+ calcd for C20H22N2: 291.1862; found: 291.1860.
8-Methyl-1-(o-tolyl)-2,3,3a,3b,4,5,6,11b-octahydro-1H-
dipyrrolo[1,2-a:3′,2′-c]quinoline (2b): colorless oil; yield: 0.11
g, 69%. IR (neat): 3063, 3024, 2926, 2871, 1599, 1495, 1468,
1254, 1106, 761, 723 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.17–
7.27 (m, 2 H), 6.95–7.01 (m, 3 H), 6.86 (d, J = 7.6 Hz, 1 H), 6.59 (t,
2855, 1556, 1512, 1463, 1397, 1277, 1107, 800, 778, 762 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.19 (d, J = 8.4 Hz, 1 H), 8.01 (d, J
= 8.4 Hz, 1 H), 7.71–7.74 (m, 2 H), 7.67 (d, J = 8.0 Hz, 1 H), 7.57
(t, J = 7.6 Hz, 2 H), 7.32–7.42 (m, 2 H), 7.27 (t, J = 7.6 Hz, 1 H),
7.05 (t, J = 7.6 Hz, 1 H), 6.80 (d, J = 8.8 Hz, 1 H), 6.57 (d, J = 8.8 Hz,
1 H), 4.46 (d, J = 5.6 Hz, 1 H), 4.16–4.21 (m, 1 H), 3.93–3.98 (m, 1
H), 3.53–3.59 (m, 1 H), 3.27–3.33 (m, 1 H), 3.13–3.18 (m, 1 H),
2.37–2.53 (m, 2 H), 2.20–2.26 (m, 1 H), 2.00–2.15 (m, 3 H),
1.87–1.94 (m, 1 H). 13C NMR (100 MHz, CDCl3): δ = 147.6, 142.8,
134.4, 134.0, 132.9, 128.4, 127.9, 127.3, 125.7, 125.5, 125.2,
125.2, 124.8, 124.6, 124.5, 123.9, 121.6, 119.2, 118.9, 63.2, 59.4,
55.0, 53.8, 36.0, 29.2, 27.5, 23.7. HRMS: m/z [M + H]+ calcd for
C
28H26N2: 391.2175; found: 391.2169.
8-Methoxy-1-(2-methoxyphenyl)-2,3,3a,3b,4,5,6,11b-octa-
hydro-1H-dipyrrolo[1,2-a:3′,2′-c]quinoline (2f): white solid;
yield: 0.11 g, 64%; mp 120–122 °C. IR (KBr): 3058, 2964, 2960,
2855, 1600, 1507, 1458, 1227, 1036, 789, 734 cm–1 1H NMR
.
(400 MHz, CDCl3): δ = 6.85–6.90 (m, 3 H), 6.61–6.67 (m, 2 H),
6.44–6.49 (m, 2 H), 5.63–5.66 (m, 1 H), 3.92 (s, 3 H), 3.82–3.86
(m, 1 H), 3.78 (s, 3 H), 3.51–3.59 (m, 2 H), 3.13–3.20 (m, 2 H),
2.80–2.86 (m, 1 H), 1.88–2.06 (m, 5 H), 1.73–1.79 (m, 1 H). 13C
NMR (100 MHz, CDCl3): δ = 150.6, 148.2, 138.6, 137.4, 126.6,
121.8, 121.3, 119.9, 118.3, 117.6, 111.3, 110.9, 59.7, 59.6, 55.9,
55.5, 51.7, 47.8, 41.2, 28.8, 23.7, 23.4. HRMS: m/z [M + H]+ calcd
for C22H26N2O2: 351.2073; found: 351.2072.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2231–2236