The Journal of Organic Chemistry
cis-7-methyl-6,7,8,8a-tetrahydro-4aH-pyrrolo[1,2-a]indol-
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122.0, 116.5, 107.8, 60.6, 53.5, 49.1, 37.1, 29.3, 24.2, 22.1,
14.2. HRMS (ESI) m/z calcd forC14H17NO3 (M+H+):
248.1287, found: 248.1284.
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9(5H)-one (1e). Petroleum/ethyl acetate (10:1) for column
chromatography. Colorless solid (67 mg, 71%), m.p. 58-
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61 °C. H NMR (400 MHz, CDCl3) δ 6.95 (d, J = 1.4 Hz, 1H),
cis-7-(Trifluoromethyl)-6,7,8,8a-tetrahydro-4aH-pyr-
rolo[1,2-a]indol-9(5H)-one (1j). Petroleum/ethyl acetate
(10:1) for column chromatography. Light yellow oil (93 mg,
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6.58 (d, J = 3.9 Hz, 1H), 6.37 (dd, J = 3.8, 2.3 Hz, 1H), 4.48 (dd,
J = 15.2, 6.8 Hz, 1H), 3.10 (td, J = 6.9, 2.2 Hz, 1H), 2.27 (dd, J
= 18.2, 6.1 Hz, 1H), 2.23 – 2.10 (m, 1H), 1.40 (M, 1H), 1.33 –
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1.07 (m, 3H), 0.99 – 0.86 (m, 1H), 0.84 (d, J = 6.3 Hz, 3H). 13
C
77%). H NMR (400 MHz, CDCl3) δ 7.07 (s, 1H), 6.74 (d, J =
3.9 Hz, 1H), 6.56 – 6.47 (m, 1H), 4.73 (dd, J = 12.8, 6.0 Hz,
1H), 3.37 – 3.25 (m, 1H), 2.50 (m, 1H), 2.31 – 2.11 (m, 2H),
1.86 – 1.71 (m, 1H), 1.63 – 1.43 (m, 3H). 13C NMR (101 MHz,
CDCl3) δ 189.8, 131.7, 127.7 (q, J = 278.6 Hz, CF3), 122.2,
117.0, 108.0, 53.3, 48.3, 35.7 (q, J = 27.1 Hz), 28.5, 20.3 (d, J
= 2.9 Hz), 18.0 (d, J = 2.5 Hz). HRMS (ESI) m/z calcd for
C12H12F3NO (M+H+): 244.0949, found: 244.0943.
NMR (101 MHz, CDCl3) δ 192.9, 131.9, 121.1, 116.0, 108.2,
53.3, 50.6, 33.0, 28.6, 27.95, 26.5, 22.34. HRMS (ESI) m/z
calcd for C12H15NO (M+H+): 190.1232, found: 190.1225.
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cis-7-Ethyl-6,7,8,8a-tetrahydro-4aH-pyrrolo[1,2-a]indol-
9(5H)-one (1f). Petroleum/ethyl acetate (10:1) for column
chromatography. Colorless solid (74 mg, 73%), m.p. 61-
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67 °C. H NMR (400 MHz, CDCl3) δ 7.03 (d, J = 1.3 Hz, 1H),
cis-9-Oxo-5,6,7,8,8a,9-hexahydro-4aH-pyrrolo[1,2-a]indol-7-
yl propionate (1k). Petroleum/ethyl acetate (10:1) for col-
umn chromatography. Light yellow oil (72 mg, 59%). 1H
NMR (400 MHz, CDCl3) δ 7.03 (t, J = 6.6 Hz, 1H), 6.74 (dd, J =
3.9, 0.8 Hz, 1H), 6.52 (dd, J = 3.9, 2.3 Hz, 1H), 4.92 (m, 1H),
4.64 (m, 1H), 3.30 (q, J = 6.9 Hz, 1H), 2.35 – 2.28 (m, 3H),
2.27 – 2.22 (m, 1H), 2.01 (m, 1H), 1.90 – 1.77 (m, 1H), 1.69
– 1.60 (m, 1H), 1.51 (m, 1H), 1.14 (t, J = 7.6 Hz, 3H). 13C NMR
(101 MHz, CDCl3) δ 190.7, 173.6, 131.6, 121.8, 116.7, 108.1,
67.7, 53.2, 48.0, 27.8, 27.6, 26.7, 25.8, 9.1. HRMS (ESI) m/z
calcd for C14H17NO3 (M+H+): 248.1287, found: 248.1287.
6.70 (d, J = 3.9 Hz, 1H), 6.48 (dd, J = 3.9, 2.3 Hz, 1H), 4.59 (dd,
J = 13.9, 7.5 Hz, 1H), 3.21 (td, J = 7.0, 2.6 Hz, 1H), 2.38 (d, J =
13.8 Hz, 1H), 2.25 (m, 1H), 1.61 – 1.48 (m, 1H), 1.40 – 1.15
(m, 5H), 1.08 – 0.96 (m, 1H), 0.88 (t, J = 7.2 Hz, 3H). 13C NMR
(101 MHz, CDCl3) δ 191.6, 131.6, 121.9, 116.0, 107.4, 54.4,
50.5, 34.0, 31.3, 29.6, 28.5, 26.5, 11.3. HRMS (EI) m/z calcd
for C13H17NO (M+): 203.1310, found: 203.1311.
cis-7-(4-Hydroxyphenyl)-6,7,8,8a-tetrahydro-4aH-pyr-
rolo[1,2-a]indol-9(5H)-one (1g). Petroleum/ethyl acetate
(2:1) for column chromatography. Off-white solid (79 mg,
59%), m.p. 128-131oC. 1H NMR (400 MHz, DMSO-d6) δ 9.21
(s, 1H), 7.40 (s, 1H), 7.01 (d, J = 8.2 Hz, 2H), 6.69 (d, J = 8.2
Hz, 2H), 6.63 (d, J = 3.7 Hz, 1H), 6.49 (d, J = 1.3 Hz, 1H), 4.76
(dd, J = 15.0, 7.1 Hz, 1H), 3.37 (m, 1H), 2.42 (m, 1H), 2.31 –
2.18 (m, 2H), 1.74 (m, 1H), 1.49 (m, 2H), 1.20 – 1.12 (m, 1H).
13C NMR (101 MHz, DMSO-d6) δ 195.8, 160.8, 141.9, 135.9,
132.6 (2C), 128.5, 120.8, 120.3 (2C), 111.9, 58.5, 55.7, 43.5,
37.9, 35.5, 34.0. HRMS (ESI) m/z calcd for C17H17NO2
(M+H+): 268.1338, found: 268.1334.
2-(cis-9-Oxo-5,6,7,8,8a,9-hexahydro-4aH-pyrrolo[1,2-a]in-
dol-7-yl)isoindoline-1,3-dione (1l). Petroleum/CH2Cl2/ethyl
acetate (6:3:1) for column chromatography. Light yellow
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solid (123 mg, 77%), m.p. 202-208 °C. H NMR (400 MHz,
CDCl3) δ 7.71 (dt, J = 7.0, 3.5 Hz, 2H), 7.65 – 7.60 (m, 2H),
7.00 (d, J = 1.2 Hz, 1H), 6.65 (d, J = 3.7 Hz, 1H), 6.44 (dd, J =
3.9, 2.2 Hz, 1H), 4.71 (dd, J = 12.9, 7.0 Hz, 1H), 4.20 – 4.07
(m, 1H), 3.34 (m, 1H), 2.59 – 2.42 (m, 2H), 2.37 – 2.25 (m,
1H), 2.03 – 1.90 (m, 1H), 1.60 – 1.41 (m, 2H). 13C NMR (101
MHz, CDCl3) δ 190.0, 168.0 (2C), 134.0 (2C), 131.8 (2C),
131.6, 123.2 (2C), 122.2, 116.7, 107.9, 53.2, 49.8, 44.4, 30.1,
24.7, 24.1. HRMS (ESI) m/z calcd for C19H16N2O3 (M+H+):
321.1239, found: 321.1237.
cis-7-Phenyl-6,7,8,8a-tetrahydro-4aH-pyrrolo[1,2-a]indol-
9(5H)-one, (1h). Petroleum/ethyl acetate (10:1) for column
chromatography. Colorless solid (94 mg, 75%), m.p. 98-
102 °C. 1H NMR (400 MHz, CDCl3) δ 7.32 – 7.26 (m, 2H), 7.23
– 7.16 (m, 3H), 7.06 (d, J = 1.3 Hz, 1H), 6.74 (d, J = 3.7 Hz,
1H), 6.50 (dd, J = 3.8, 2.3 Hz, 1H), 4.66 (dd, J = 15.3, 6.9 Hz,
1H), 3.31 (td, J = 7.0, 1.5 Hz, 1H), 2.66 – 2.59 (m, 1H), 2.53 –
2.47 (m, 1H), 2.45 – 2.38 (m, 1H), 1.84 – 1.69 (m, 2H), 1.64
– 1.54 (m, 1H), 1.44 – 1.33 (m, 1H). 13C NMR (101 MHz,
CDCl3) δ 190.9, 146.2, 131.4, 128.5 (2C), 126.8 (2C), 126.4,
122.2, 116.2, 107.7, 53.9, 51.0, 39.2, 32.8, 30.5, 28.4. HRMS
(ESI) m/z calcd for C17H17NO (M+H+): 252.1388, found:
252.1382.
N-(cis-9-Oxo-5,6,7,8,8a,9-hexahydro-4aH-pyrrolo[1,2-a]in-
dol-7-yl)acetamide (1m). CH2Cl2/CH3OH (10:1) for column
chromatography. Light yellow solid (81 mg, 70%), m.p. 202-
205 °C. 1H NMR (400 MHz, CD3OD) δ 7.21 (s, 1H), 6.70 (d, J
= 3.9 Hz, 1H), 6.58 – 6.48 (m, 1H), 4.71 (dd, J = 13.7, 7.0 Hz,
1H), 3.67 (m, 1H), 3.36 (m, 1H), 2.48 – 2.30 (m, 2H), 1.94 (s,
3H), 1.73 (m, 2H), 1.47 – 1.34 (m, 2H). 13C NMR (101 MHz,
CD3OD) δ 193.0,172.5,132.3, 124.6, 117.9, 109.4, 54.8, 51.1,
45.3, 30.8, 29.0, 28.2, 23.2. HRMS (ESI) m/z calcd for
C13H16N2O2 (M+H+): 233.1290, found: 233.1285.
cis-Ethyl 9-oxo-5,6,7,8,8a,9-hexahydro-4aH-pyrrolo[1,2-a]in-
dole-7-carboxylate (1i). Petroleum/ethyl acetate (7:1) for
column chromatography. Light yellow oil (90 mg, 73%). 1H
NMR (400 MHz, CDCl3) δ 7.07 (d, J = 1.2 Hz, 1H), 6.72 – 6.67
(m, 1H), 6.50 (dd, J = 3.9, 2.3 Hz, 1H), 4.68 (dd, J = 13.0, 7.2
Hz, 1H), 4.12 (q, J = 7.2 Hz, 2H), 3.27 (m, 1H), 2.52 – 2.44 (m,
1H), 2.42 – 2.33 (m, 1H), 2.32 – 2.23 (m, 1H), 1.92 (m, 1H),
1.64 (dt, J = 12.1, 4.5 Hz, 2H), 1.53 – 1.42 (m, 1H), 1.25 (t, J =
7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 190.5, 175.2, 131.6,
cis-2,3-Dimethyl-2,3-dihydro-1H-pyrrolizin-1-one (1n). Pe-
troleum/ethyl acetate (10:1) for column chromatography.
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Light yellow oil (31 mg, 42%). H NMR (400 MHz, CDCl3) δ
7.02 (d, J = 1.3 Hz, 1H), 6.71 (d, J = 3.9 Hz, 1H), 6.52 (dd, J =
3.9, 2.3 Hz, 1H), 4.17 – 4.06 (m, 1H), 2.69 (qd, J = 7.4, 4.8 Hz,
1H), 1.62 (d, J = 6.5 Hz, 3H), 1.35 (d, J = 7.4 Hz, 3H). 13C NMR
(101 MHz, CDCl3) δ 191.9, 132.1, 120.9, 116.7, 107.7, 58.2,
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