The Journal of Organic Chemistry
Note
= 10.8, 7.1 Hz, 1H), 2.30 (s, 3H), 1.95 (s, 3H), 1.17 (t, J = 7.1 Hz,
3H); 13C{1H} NMR (101 MHz, CDCl3) δ 201.2, 201.1, 171.6, 162.9
(d, JCF = 247.6 Hz), 137.6 (d, JCF = 7.3 Hz), 130.6 (d, JCF = 8.3 Hz),
124.1 (d, JCF = 3.0 Hz), 115.3 (d, JCF = 22.1 Hz), 115.2 (d, JCF = 21.0
Hz), 71.1, 61.7, 50.5 (d, JCF = 1.6 Hz), 30.4, 29.9, 13.9; HRMS (EI-
TOF, m/z) calcd for C15H17FO4 [M]+ 280.1111, found 280.1112.
Ethyl 3-Acetyl-2-(3-nitrophenyl)-4-oxopentanoate (4m):
eluent = petroleum ether/ethyl acetate (3:2), white solid, 79% yield
(m, 2H), 7.40 (dd, J = 8.5, 1.8 Hz, 1H), 4.76 (d, J = 11.8 Hz, 1H),
4.57 (d, J = 11.8 Hz, 1H), 4.15 (dq, J = 10.8, 7.1 Hz, 1H), 4.02 (dq, J
= 10.8, 7.1 Hz, 1H), 2.33 (s, 3H), 1.90 (s, 3H), 1.14 (t, J = 7.1 Hz,
3H); 13C{1H} NMR (101 MHz, CDCl3) δ 201.7, 201.5, 172.1, 133.4,
132.9, 132.6, 129.0, 128.0, 127.7(0), 127.6(5), 126.6, 126.4, 125.7,
71.2, 61.6, 51.0, 30.4, 30.0, 13.9; HRMS (EI-TOF, m/z) calcd for
C19H20O4 [M]+ 312.1362, found 312.1363.
Ethyl 3-Acetyl-2-(furan-2-yl)-4-oxopentanoate (4t): eluent =
1
petroleum ether/ethyl acetate (3:1), white solid, 68% yield (85.8 mg);
(121.4 mg); mp 119.2−120.1 °C; H NMR (400 MHz, CDCl3) δ
1
mp 49.1−50.2 °C; H NMR (400 MHz, CDCl3) δ 7.35 (d, J = 1.2
8.26−8.10 (m, 2H), 7.64 (dd, J = 5.1, 3.9 Hz, 1H), 7.57−7.51 (m,
1H), 4.69 (d, J = 11.7 Hz, 1H), 4.56 (d, J = 11.7 Hz, 1H), 4.16 (dq, J
= 10.8, 7.1 Hz, 1H), 4.05 (dq, J = 10.8, 7.1 Hz, 1H), 2.36 (s, 3H),
2.01 (s, 3H), 1.17 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 200.6, 200.4, 171.1, 148.6, 137.5, 134.8, 130.1, 123.2, 123.1,
70.9, 62.0, 50.6, 30.5, 30.2, 13.9; HRMS (EI-TOF, m/z) calcd for
C15H17NO6 [M]+ 307.1056, found 307.1067.
Hz, 1H), 6.32 (dd, J = 3.2, 1.9 Hz, 1H), 6.22 (d, J = 3.2 Hz, 1H), 4.66
(d, J = 11.7 Hz, 1H), 4.58 (d, J = 11.7 Hz, 1H), 4.20−4.06 (m, 2H),
2.29 (s, 3H), 2.04 (s, 3H), 1.21 (t, J = 7.1 Hz, 3H); 13C{1H} NMR
(101 MHz, CDCl3) δ 201.4, 201.2, 169.8, 148.3, 142.7, 110.9, 108.8,
68.6, 61.9, 44.7, 29.9, 29.5, 14.0; HRMS (EI-TOF, m/z) calcd for
C13H16O5 [M]+ 252.0998, found 252.0999.
Ethyl (E)-3-Acetyl-4-oxo-2-styrylpentanoate (4u): eluent =
Ethyl 3-Acetyl-4-oxo-2-(o-tolyl)pentanoate (4n): eluent =
petroleum ether/ethyl acetate (3:2), yellow solid, 79% yield (113.9
petroleum ether/ethyl acetate (3:1), white viscous liquid, 80% yield
1
1
mg); mp 65.9−66.8 °C; H NMR (400 MHz, CDCl3) δ 7.34−7.25
(110.5 mg); H NMR (400 MHz, CDCl3) δ 7.25−7.21 (m, 1H),
(m, 5H), 4.63 (d, J = 11.8 Hz, 1H), 4.39 (d, J = 11.8 Hz, 1H), 4.13
(dq, J = 10.8, 7.1 Hz, 1H), 4.07−3.98 (m, 1H), 2.29 (s, 3H), 1.90 (s,
3H), 1.16 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ
201.8, 201.7, 171.8, 135.9, 135.2, 128.7 (2C), 128.2, 126.5 (2C),
122.6, 70.2, 61.6, 48.6, 30.0, 29.8, 14.1; HRMS (EI-TOF, m/z) calcd
for C17H20O4 [M]+ 288.1362, found 288.1360.
7.20−7.12 (m, 3H), 4.77−4.68 (m, 2H), 4.11 (dq, J = 10.8, 7.1 Hz,
1H), 3.99 (dq, J = 10.8, 7.1 Hz, 1H), 2.45 (s, 3H), 2.31 (s, 3H), 1.88
(s, 3H), 1.14 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3)
δ 201.7, 201.4, 172.5, 137.1, 133.7, 131.2, 127.9, 126.8, 126.5, 70.4,
61.4, 45.9, 30.6, 30.0, 19.9, 13.9; HRMS (EI-TOF, m/z) calcd for
C16H20O4 [M]+ 276.1362, found 276.1364.
Ethyl 3-Acetyl-2-cyclohexyl-4-oxopentanoate (4v): eluent =
petroleum ether/ethyl acetate (1:1); yellow solid, 43% yield (57.7
mg); mp 48.3−50.7 °C; H NMR (400 MHz, CDCl3) δ 4.26 (d, J =
Ethyl 3-Acetyl-2-(2-fluorophenyl)-4-oxopentanoate (4o):
eluent = petroleum ether/ethyl acetate (3:1), white solid, 73% yield
(102.3 mg); mp 50.7−51.9 °C; 1H NMR (400 MHz, CDCl3) δ 7.30−
7.23 (m, 2H), 7.14−7.03 (m, 2H), 4.77 (d, J = 11.7 Hz, 1H), 4.65 (d,
J = 11.7 Hz, 1H), 4.15−4.03 (m, 2H), 2.33 (s, 3H), 1.97 (s, 3H), 1.15
(t, J = 7.1 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 201.4,
201.3, 171.3, 160.5 (d, JCF = 247.5 Hz), 130.2 (d, JCF = 3.6 Hz), 129.9
(d, JCF = 8.3 Hz), 124.7 (d, JCF = 3.6 Hz), 122.6 (d, JCF = 14.8 Hz),
1
11.5 Hz, 1H), 4.13 (pd, J = 7.6, 3.7 Hz, 2H), 3.24 (dd, J = 11.5, 2.4
Hz, 1H), 2.21 (s, 3H), 2.20 (s, 3H), 1.70 (dd, J = 28.2, 14.6 Hz, 4H),
1.35−1.23 (m, 6H), 1.23−1.04 (m, 3H), 0.90−0.80 (m, 1H);
13C{1H} NMR (101 MHz, CDCl3) δ 202.7, 202.4, 172.5, 69.4, 60.6,
50.4, 38.8, 32.1, 29.9, 28.6(7), 28.6(5), 26.6, 26.3, 26.0, 14.2; HRMS
(EI-TOF, m/z) calcd for C15H24O4 [M]+ 268.1675, found 268.1681.
4-Ethyl 1-Methyl 2-Acetyl-3-phenylsuccinate (5a): eluent =
petroleum ether/ethyl acetate (3:1), white solid, 78% yield (108.5
116.0 (d, JCF = 22.1 Hz), 70.1 (d, JCF = 1.1 Hz), 61.7, 44.4 (d, JCF
=
1.6 Hz), 30.1, 29.3, 13.9; HRMS (EI-TOF, m/z) calcd for C15H17FO4
[M]+ 280.1111, found 280.1110.
1
Ethyl 3-Acetyl-2-(3,5-dimethoxyphenyl)-4-oxopentanoate
(4p): eluent = petroleum ether/ethyl acetate (2:1), white solid,
mg); mp 69.3−71.7 °C; dr = 61:39; H NMR (400 MHz, CDCl3) δ
7.33−7.24 (m, 5H), 4.46−4.30 (m, 2H), 4.20−4.10 (m, 1H), 4.10−
3.98 (m, 1H), 3.75 (s, 1.16H), 3.49 (s, 1.84H), 2.35 (s, 1.84H), 1.95
(s, 1.16H), 1.17 (dd, J = 13.3, 7.0 Hz, 3H); 13C{1H} NMR (101
MHz, CDCl3) δ 201.4, 200.9, 172.2, 172.1, 168.3, 167.2, 135.4, 135.1,
129.0, 128.8, 128.3, 128.2, 128.1, 127.9, 63.1, 61.7, 61.4, 52.8, 52.6,
50.4, 50.3, 31.6, 29.6, 14.0, 13.9; HRMS (EI-TOF, m/z) calcd for
C15H18O5 [M]+ 278.1154, found 278.1155.
1
81% yield (130.6 mg); mp 100.6−102.0 °C; H NMR (400 MHz,
CDCl3) δ 6.40 (d, J = 2.2 Hz, 2H), 6.36 (t, J = 2.2 Hz, 1H), 4.60 (d, J
= 11.8 Hz, 1H), 4.30 (d, J = 11.8 Hz, 1H), 4.15 (dq, J = 10.8, 7.1 Hz,
1H), 4.04 (dq, J = 10.8, 7.1 Hz, 1H), 3.77 (s, 6H), 2.28 (s, 3H), 1.96
(s, 3H), 1.18 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3)
δ 201.7, 201.4, 171.9, 161.1 (2C), 137.3, 106.4 (2C), 99.9, 71.1, 61.5,
55.4 (2C), 51.0, 30.4, 29.9, 13.9; HRMS (EI-TOF, m/z) calcd for
C17H22O6 [M]+ 322.1416, found 322.1417.
Diethyl 2-Acetyl-3-phenylsuccinate (5b): eluent = petroleum
ether/ethyl acetate (3:1), white solid, 80% yield (116.9 mg); mp
71.5−72.8 °C; dr = 68:32; 1H NMR (400 MHz, CDCl3) δ 7.33−7.25
(m, 5H), 4.43−4.29 (m, 2H), 4.23−4.12 (m, 1.6H), 4.09−3.99 (m,
1H), 3.99−3.90 (m, 1.4H), 2.34 (s, 2.1H), 1.97 (s, 0.9H), 1.27 (t, J =
7.1 Hz, 0.9H), 1.17 (td, J = 7.1, 5.3 Hz, 3H), 0.99 (t, J = 7.1 Hz,
2.1H); 13C{1H} NMR (101 MHz, CDCl3) δ 201.4, 201.0, 172.3,
172.1, 167.8, 166.8, 135.4, 135.2, 129.0, 128.7, 128.4, 128.3, 128.1,
127.9, 63.2, 62.0, 61.9, 61.6, 61.4, 50.4, 50.2, 31.5, 29.4, 14.0(0),
13.9(6), 13.9, 13.8; HRMS (EI) calcd for C16H20O5 [M]+ 292.1311,
found 292.1309.
4-Ethyl 1-(2-Methoxyethyl) 2-Acetyl-3-phenylsuccinate
(5c): eluent = petroleum ether/ethyl acetate (2:1), white viscous
liquid, 72% yield (116.0 mg); dr = 66:34; 1H NMR (400 MHz,
CDCl3) δ 7.33−7.25 (m, 5H), 4.45 (dd, J = 11.6, 10.0 Hz, 1H),
4.38−4.27 (m, 1.7H), 4.19−4.11 (m, 1H), 4.11−3.97 (m, 2.4H),
3.65−3.53 (m, 0.8H), 3.37 (d, J = 3.4 Hz, 1.2H), 3.35−3.32 (m,
0.5H), 3.31−3.25 (m, 0.7H), 3.24 (s, 1.9H), 2.36 (s, 2H), 1.98 (s,
1H), 1.17 (td, J = 7.1, 3.3 Hz, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 201.2, 200.8, 172.2, 172.1, 167.9, 166.8, 135.4, 135.1, 129.0,
128.7, 128.4, 128.3, 128.1, 127.9, 70.1, 69.9, 64.6, 64.3, 63.1, 61.8,
61.4, 58.9, 58.8, 50.4, 50.2, 31.5, 29.5, 13.9; HRMS (EI-TOF, m/z)
calcd for C17H22O6 [M]+ 322.1416, found 322.1412.
Ethyl 3-Acetyl-4-oxo-2-(3,4,5-trimethoxyphenyl)-
pentanoate (4q): eluent = petroleum ether/ethyl acetate (2:1),
1
white solid, 77% yield (135.7 mg); mp 121.2−122.3 °C; H NMR
(400 MHz, CDCl3) δ 6.46 (s, 2H), 4.61 (d, J = 11.7 Hz, 1H), 4.30 (d,
J = 11.7 Hz, 1H), 4.17 (dq, J = 10.8, 7.1 Hz, 1H), 4.10−4.02 (m, 1H),
3.84 (s, 6H), 3.82 (s, 3H), 2.28 (s, 3H), 1.96 (s, 3H), 1.20 (t, J = 7.1
Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 201.8, 201.3, 172.0,
153.5 (2C), 137.7, 130.5, 105.3 (2C), 71.1, 61.6, 60.8, 56.2 (2C),
50.9, 30.5, 29.9, 14.0; HRMS (EI-TOF, m/z) calcd for C18H24O7
[M]+ 352.1522, found 352.1523.
Ethyl 3-Acetyl-2-(benzo[d][1,3]dioxol-5-yl)-4-oxopenta-
noate (4r): eluent = petroleum ether/ethyl acetate (5:2), yellow
solid, 83% yield (127.1 mg); mp 91.3−92.6 °C; 1H NMR (400 MHz,
CDCl3) δ 6.73 (ddd, J = 9.6, 8.4, 1.5 Hz, 3H), 5.95 (q, J = 1.5 Hz,
2H), 4.56 (d, J = 11.8 Hz, 1H), 4.29 (d, J = 11.8 Hz, 1H), 4.13 (ddd, J
= 14.3, 9.0, 5.4 Hz, 1H), 4.03 (dq, J = 10.8, 7.1 Hz, 1H), 2.28 (s, 3H),
1.97 (s, 3H), 1.18 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 201.7, 201.5, 172.1, 148.2, 147.5, 128.6, 121.8, 108.7, 108.4,
101.3, 71.3, 61.5, 50.4, 30.3, 29.9, 14.0; HRMS (EI-TOF, m/z) calcd
for C16H18O6 [M]+ 306.1103, found 306.1101.
Ethyl 3-Acetyl-2-(naphthalen-2-yl)-4-oxopentanoate (4s):
eluent = petroleum ether/ethyl acetate (3:1), white solid, 88% yield
4-Ethyl 1-Methyl 2-(Cyclopropanecarbonyl)-3-phenylsucci-
nate (5d): eluent = petroleum ether/ethyl acetate (2:1), white
viscous liquid, 58% yield (88.3 mg); dr > 20:1; 1H NMR (400 MHz,
1
(137.4 mg); mp 109.0−110.7 °C; H NMR (400 MHz, CDCl3) δ
7.81 (dd, J = 8.7, 2.7 Hz, 3H), 7.73 (d, J = 1.2 Hz, 1H), 7.53−7.45
9920
J. Org. Chem. 2021, 86, 9914−9923