10.1002/ejoc.201801530
European Journal of Organic Chemistry
FULL PAPER
2-(3-(1-bromo-2-oxo-4-phenylcyclopent-3-en-1-yl)propyl)isoindoline-
1,3-dione (5af): Yield: 85% (181 mg), colorless solid, mp 122-124 °C; 1H
NMR (600 MHz, CDCl3): δ 7.82-7.79 (m, 2H), 7.70-7.68 (m, 2H), 7.60-
7.59 (m, 2H), 7.50-7.43 (m, 3H), 6.57 (t, 1H, J = 1.7 Hz), 3.76-3.70 (m,
2H), 3.57 (dd, 1H, J = 18.7, 1.5 Hz), 3.42 (dd, 1H, J = 18.9, 2.0 Hz), 2.23-
2.18 (m, 1H), 2.06-2.01 (m, 1H), 1.91-1.79 (m, 2H); 13C NMR (150 MHz,
CDCl3): δ 202.2, 168.8, 168.2, 134.0, 132.8, 132.1, 132.1, 129.1, 127.1,
123.3, 123.3, 61.7, 46.0, 37.5, 36.5, 25.3; HRMS (ESI) calcd. for
C22H1879BrNO3Na [M+Na]+: 446.0362, found 446.0362.
= 18.8 Hz), 3.46 (d, 1H, J = 18.8 Hz), 2.34-2.29 (m, 1H), 2.20-2.14 (m,
1H), 2.06-2.01 (m, 1H), 1.98-1.92 (m, 1H); 13C NMR (150 MHz, CDCl3): δ
202.2, 168.8, 164.4, 150.4, 135.2, 132.5, 132.1, 130.6, 129.0, 127.0,
123.4, 123.1, 65.0, 61.4, 45.8, 35.7, 25.3; HRMS (ESI) calcd. for
C21H1879BrNO5Na [M+Na]+: 466.0261, found 466.0249.
5-bromo-5-(3-phenoxypropyl)-3-phenylcyclopent-2-en-1-one (5am):
1
Yield: 32% (60 mg), colorless solid, mp 102-104 °C; H NMR (400 MHz,
CDCl3): δ 7.65-7.63 (m, 2H), 7.52-7.46 (m, 3H), 7.29-7.25 (m, 2H), 6.94 (t,
1H, J = 7.3 Hz), 6.87 (d, 2H, J = 7.9 Hz), 6.63 (t, 1H, J = 1.6 Hz), 4.06-
3.97 (m, 2H), 3.65 (dd, 1H, J = 19.0, 1.4 Hz), 3.50 (dd, 1H, J = 19.0, 1.9
Hz), 2.38-2.32 (m, 1H), 2.16-2.05 (m, 2H), 1.99-1.91 (m, 1H); 13C NMR
(100 MHz, CDCl3): δ 202.6, 168.9, 158.7, 132.9, 132.1, 129.5, 129.1,
127.1, 123.4, 120.8, 114.5, 67.0, 62.2, 46.1, 36.0, 26.1; HRMS (ESI)
calcd. for C20H2079BrO2 [M+H]+: 371.0641, found 371.0638.
N-(3-(1-bromo-2-oxo-4-phenylcyclopent-3-en-1-yl)propyl)-4-methyl-
N-phenylbenzenesulfonamide (5ag): Yield: 80% (210 mg), colorless
solid, mp 156-157 °C; 1H NMR (600 MHz, CDCl3): δ 7.59-7.57 (m, 2H),
7.52-7.49 (m, 1H), 7.47-7.43 (m, 4H), 7.30-7.28 (m, 3H), 7.23 (d, 2H, J =
8.0 Hz), 7.04-7.02 (m, 2H), 6.55 (t, 1H, J = 1.6 Hz), 3.63-3.56 (m, 2H),
3.52 (dd, 1H, J = 18.9, 1.4 Hz), 3.29 (dd, 1H, J = 18.8, 1.9 Hz), 2.41 (s,
3H), 2.22-2.16 (m, 1H), 1.98-1.93 (m, 1H), 1.80-1.75 (m, 1H), 1.62-1.56
(m, 1H); 13C NMR (150 MHz, CDCl3): δ 202.4, 168.9, 143.6, 138.9, 134.9,
132.8, 132.1, 129.5, 129.1, 129.1, 128.7, 128.1, 127.7, 127.1, 123.1,
62.0, 50.0, 46.1, 36.1, 24.9, 21.6; HRMS (ESI) calcd. for
C27H2679BrNO3SNa [M+Na]+: 546.0709, found 546.0717.
5-bromo-5-(3-(4-bromophenoxy)propyl)-3-phenylcyclopent-2-en-1-
one (5am’): Yield: 35% (79 mg), colorless solid, mp 127-129 °C; 1H NMR
(400 MHz, CDCl3): δ 7.65-7.63 (m, 2H), 7.53-7.46 (m, 3H), 7.37-7.34 (m,
2H), 6.76-6.74 (m, 2H), 6.63 (t, 1H, J = 1.5 Hz), 4.04-3.94 (m, 2H), 3.65
(dd, 1H, J = 19.0, 1.4 Hz), 3.48 (dd, 1H, J = 19.0, 1.9 Hz), 2.37-2.30 (m,
1H), 2.13-2.03 (m, 2H), 1.96-1.89 (m, 1H); 13C NMR (100 MHz, CDCl3): δ
202.5, 168.9, 157.8, 132.9, 132.3, 132.1, 129.2, 127.1, 123.3, 116.3,
113.0, 67.4, 62.0, 46.1, 35.9, 26.0; HRMS (ESI) calcd. for C20H1979Br2O2
[M+H]+: 448.9746, found 448.9754.
4-(1-bromo-2-oxo-4-phenylcyclopent-3-en-1-yl)-N-methoxy-N-
methylbutanamide (5ah): Yield: 78% (143 mg), pale-yellow oil; 1H NMR
(600 MHz, CDCl3): δ 7.64-7.62 (m, 2H), 7.51-7.44 (m, 3H), 6.60 (t, 1H, J
= 1.6 Hz), 3.66 (s, 3H), 3.59-3.58 (m, 2H), 3.15 (s, 3H), 2.52-2.49 (m, 2H),
2.21-2.15 (m, 1H), 1.94-1.88 (m, 2H), 1.77-1.72 (m, 1H); 13C NMR (150
MHz, CDCl3): δ 202.8, 169.3, 132.9, 132.1, 129.1, 127.2, 123.3, 62.3,
61.3, 45.7, 38.6, 32.2, 31.2, 20.8; HRMS (ESI) calcd. for C17H2179BrNO3
[M+H]+: 366.0699, found 366.0684.
5-bromo-5-methyl-3-(p-tolyl)cyclopent-2-en-1-one (5an): Yield: 62%
1
(83 mg), yellow solid, mp 107-108 °C; H NMR(600 MHz, CDCl3): δ 7.54
(d, 2H, J = 8.2 Hz), 7.29 (d, 2H, J = 8.0 Hz), 6.56 (t, 1H, J = 1.7 Hz), 3.75
(dd, 1H, J = 18.7, 1.5 Hz), 3.40 (dd, 1H, J = 18.7, 1.9 Hz), 2.43 (s, 3H),
1.91(s, 3H); 13C NMR (150 MHz, CDCl3): δ 202.9, 168.5, 142.9, 130.2,
129.8, 127.1, 121.8, 57.6, 48.5, 27.7, 21.6; HRMS (ESI) calcd. for
C13H1479BrO [M+H]+: 265.0223, found 265.0225.
5-bromo-3-phenyl-5-(3-tosylpropyl)cyclopent-2-en-1-one (5ai): Yield:
72% (156 mg), colorless solid, mp 134-135 °C; 1H NMR (400 MHz,
CDCl3): δ 7.78 (d, 2H, J = 8.1 Hz), 7.63 (d, 2H, J = 6.8 Hz), 7.55-7.46 (m,
3H), 7.35 (d, 2H, J =8.0 Hz), 6.59 (s, 1H), 3.61 (d, 1H, J = 19.0 Hz), 3.44
(dd, 1H, J = 18.9, 1.5 Hz), 3.17-3.08 (m, 2H), 2.44 (s, 3H), 2.22-2.10 (m,
2H), 1.99-1.90 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 202.0, 169.0,
144.9, 136.1, 132.7, 132.2, 130.0, 129.2, 128.0, 127.1, 123.1, 61.2, 55.8,
45.9, 37.6, 21.6, 19.6; HRMS (ESI) calcd. for C21H2179BrO3SNa [M+Na]+:
455.0287, found 455.0281.
5-bromo-3-(4-fluorophenyl)-5-methylcyclopent-2-en-1-one
(5ao):
Yield: 74% (100 mg), colorless solid, mp 104-105 °C; 1H NMR (600 MHz,
CDCl3): δ 7.64-7.62 (m, 2H), 7.15 (t, 2H, J = 8.6 Hz), 6.53 (t, 1H, J = 1.6
Hz), 3.71 (dd, 1H, J = 18.7, 1.5 Hz), 3.38 (dd, 1H, J =18.7, 1.9 Hz), 1.88
(s, 3H); 13C NMR (150 MHz, CDCl3): δ 202.6, 167.0, 164.9 (d, 1C, J =
252.8 Hz), 129.3, 129.3 (d, 1C, J = 6.0 Hz), 122.5 (d, 1C, J = 1.5 Hz),
116.4 (d, 1C, J = 21.9 Hz), 57.3, 48.6, 27.6; HRMS (ESI) calcd. for
C12H1179BrFO [M+H]+: 268.9972, found 268.9981.
ethyl 4-(1-bromo-2-oxo-4-phenylcyclopent-3-en-1-yl)butanoate (5aj):
1
Yield: 61% (108 mg), pale-yellow solid, mp 63-65 °C; H NMR (400 MHz,
CDCl3): δ 7.64-7.62 (m, 2H), 7.52-7.44 (m, 3H), 6.60 (t, 1H, J = 1.6 Hz),
4.11 (q, 2H, J = 8.0 Hz), 3.55 (qd, 2H, J = 19.0, 1.5 Hz), 2.42-2.30 (m,
2H), 2.20-2.14 (m, 1H), 1.97-1.86 (m, 2H), 1.78-1.69 (m, 1H), 1.24 (t, 3H,
J = 7.1 Hz); 13C NMR (100 MHz, CDCl3): δ 202.5, 173.0, 169.0, 132.9,
132.1, 129.1, 127.1, 123.3, 61.9, 60.5, 45.8, 38.4, 33.6, 21.3, 14.2;
HRMS (ESI) calcd. for C17H2079BrO3 [M+H]+: 351.0590, found 351.0599.
5-bromo-3-(4-chlorophenyl)-5-methylcyclopent-2-en-1-one
(5ap):
Yield: 80% (115 mg), colorless solid, mp 117-118 °C; 1H NMR (600 MHz,
CDCl3): δ 7.55 (dd, 2H, J = 6.6, 1.9 Hz), 7.42 (dd, 2H, J = 6.7, 2.0 Hz),
6.55 (t, 1H, J = 1.8 Hz), 3.69 (dd, 1H, J = 18.7, 1.3 Hz), 3.37 (dd, 1H, J =
18.7, 1.9 Hz), 1.88 (s, 3H); 13C NMR (150 MHz, CDCl3): δ 202.6, 166.9,
138.1, 131.4, 129.4, 128.3, 123.1, 57.2, 48.5, 27.5; HRMS (ESI) calcd.
for C12H1179Br35ClO [M+H]+: 284.9676, found 284.9685.
3-(1-bromo-2-oxo-4-phenylcyclopent-3-en-1-yl)propyl acetate (5ak):
Yield: 82% (139 mg), colorless solid, mp 74-76 °C; 1H NMR (600
MHz,CDCl3): δ 7.63-7.62 (m, 2H), 7.51-7.44 (m, 3H), 6.60 (t, 1H, J = 1.7
Hz), 4.11-4.08 (m, 2H), 3.61 (dd, 1H, J = 18.9, 1.5 Hz), 3.42 (dd, 1H, J =
18.9, 2.0 Hz), 2.23-2.18 (m, 1H), 2.02 (s, 3H), 1.99-1.88 (m, 2H), 1.79-
1.72 (m, 1H); 13C NMR (150 MHz,CDCl3): δ 202.5, 171.1, 168.9, 132.8,
132.2, 129.2, 127.1, 123.2, 63.7, 61.8, 46.0, 35.8, 25.4, 21.0; HRMS
(ESI) calcd. for C16H1879BrO3 [M+H]+: 337.0434, found 337.0425.
5-bromo-3-(4-bromophenyl)-5-methylcyclopent-2-en-1-one
(5aq):
Yield: 68% (113 mg), colorless solid, mp 111-113 °C; 1H NMR (600 MHz,
CDCl3): δ 7.59 (d, 2H, J = 8.4 Hz), 7.47 (d, 2H, J = 8.5 Hz), 6.57 (t, 1H, J
= 1.4 Hz), 3.69 (dd, 1H, J = 18.7, 1.3 Hz), 3.37 (dd, 1H, J =18.7, 1.9 Hz),
1.88 (s, 3H); 13C NMR (150 MHz, CDCl3): δ 202.6, 166.9, 132.4, 131.9,
128.4, 126.6, 123.2, 57.6, 48.4, 27.5; HRMS (ESI) calcd. for
C12H1079Br2ONa [M+Na]+: 350.8991, found 350.8979.
3-(1-bromo-2-oxo-4-phenylcyclopent-3-en-1-yl)propyl
4-
5-bromo-5-methyl-3-(4-(trifluoromethyl)phenyl)cyclopent-2-en-1-one
(5ar): Yield: 84% (134 mg), colorless solid, mp 100-101 °C; 1H NMR (400
MHz, CDCl3): δ 7.74 (s, 4H), 6.68 (t, 1H, J = 1.6 Hz), 3.75 (dd, 1H, J =
18.9, 1.5 Hz), 3.42 (dd, 1H, J = 18.9, 2.0 Hz), 1.92 (s, 3H); 13C NMR (100
nitrobenzoate (5al): Yield: 90% (200 mg), colorless solid, mp 118-
119 °C;1H NMR (600 MHz, CDCl3): δ 8.22-8.25 (m, 4H), 7.64 (d, 2H, J =
7.4 Hz), 7.53-7.46 (m, 3H), 6.63 (s, 1H), 4.44-4.42 (m, 2H), 3.66 (d, 1H, J
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