Baoqiang Wan et al.
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ylphenyl iodide (164.1 mg, 0.75 mmol), and 1c (115.0 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2g (eluent: petrole-
um ether/ethyl ether=10/1) as a white solid; yield: 120.1 mg
(75%); mp 110–1118C (ethyl ether/petroleum ether).
1H NMR (300 MHz, CDCl3): d=8.01 (d, J=7.5 Hz, 2H, Ar-
H), 7.55 (t, J=7.4 Hz, 1H, Ar-H), 7.43 (t, J=7.7 Hz, 2H,
Ar-H), 7.24 (d, J=7.5 Hz, 2H, Ar-H), 7.15 (d, J=8.1 Hz,
2H, Ar-H), 6.00 (t, J=8.1 Hz, 1H, =CH), 4.59 (t, J=
11.4 Hz, 1H, one proton from OCH2), 4.36 (dd, J1 =11.7 Hz,
J2 =4.2 Hz, 1H, O2CCH), 4.15–4.05 (m, 1H, one proton
(dd, J1 =11.7 Hz, J2 =4.2 Hz, 1H, O2CCH), 4.15–4.00 (m,
1H, one proton from OCH2), 3.73 [t, J=12.5 Hz, 1H, one
proton from C=C(Ar)CH2], 2.92–2.75 [m, 2H, one proton
from C=C(Ar)CH2 and one proton from ArC=CCH2], 2.35
(s, 3H, CH3), 2.28–2.14 (m, 1H, one proton from ArC=
CCH2); 13C NMR (75.4 MHz, CDCl3): d=192.0, 173.0,
142.6, 142.3, 137.9, 135.6, 133.6, 128.59, 128.55, 128.3, 128.2,
127.2, 126.1, 123.5, 68.6, 59.1, 31.3, 29.8, 21.3; IR (neat): n=
1742, 1684, 1597, 1580, 1486, 1448, 1363, 1325, 1282, 1249,
1212, 1182, 1141, 1103, 1047, 1017 cmꢀ1; MS (70 eV, EI): m/z
from OCH2), 3.73 [t, J=12.5 Hz, 1H, one proton from C= (%)=320 (M+, 0.74), 105 (100); anal. calcd. for C21H20O3
C(Ar)CH2], 2.95–2.77 [m, 2H, one proton from C= (%): C 78.73, H 6.29; found: C 78.94, H 6.64.
C(Ar)CH2 and one proton from ArC=CCH2], 2.35 (s, 3H,
CH3), 2.30–2.17 (m, 1H, one proton from ArC=CCH2);
Synthesis of 3-Benzoyl-5-(3,4-dimethylphenyl)-5(E)-
3,4,7,8-tetrahydro-2H-oxocin-2-one (2j)
13C NMR (75.4 MHz, CDCl3): d=192.1, 173.0, 142.4, 139.4,
137.3, 135.7, 133.7, 129.1, 128.7, 128.6, 126.3, 125.6, 68.8,
59.1, 31.3, 29.9, 21.0; IR (neat): n=1738, 1683, 1596, 1514,
1465, 1447, 1360, 1324, 1278, 1254, 1205, 1192, 1177, 1144,
1057, 1014 cmꢀ1; MS (70 eV, EI): m/z (%)=320 (M+, 2.57),
105 (100); anal. calcd. for C21H20O3 (%): C 78.73, H 6.29;
found: C 78.44, H 6.29.
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.7 mg, 0.025 mmol), PPh3
(13.3 mg, 0.050 mmol), K2CO3 (138.5 mg, 1.0 mmol), 3,4-di-
methylphenyl iodide (174.5 mg, 0.75 mmol), and 1c
(113.9 mg, 0.50 mmol) in 4 mL of CH3CN afforded 2j
[eluent: petroleum ether (b.p. 30–608C)/ethyl ether=10/1]
as an oil; yield: 119.2 mg (72%). 1H NMR (300 MHz,
CDCl3): d=8.01 (d, J=7.8 Hz, 2H, Ar-H), 7.54 (t, J=
7.2 Hz, 1H, Ar-H), 7.42 (t, J=7.7 Hz, 2H, Ar-H), 7.16–7.04
(m, 3H, Ar-H), 6.00 (t, J=8.0 Hz, 1H, =CH), 4.58 (t, J=
11.4 Hz, 1H, one proton from OCH2), 4.36 (dd, J1 =11.6 Hz,
J2 =4.1 Hz, 1H, O2CCH), 4.15–4.05 (m, 1H, one proton
from OCH2), 3.72 [t, J=12.3 Hz, 1H, one proton from C=
C(Ar)CH2], 2.95–2.78 [m, 2H, one proton from C=
C(Ar)CH2 and one proton from ArC=CCH2], 2.35–2.17 (m,
7H, one proton from ArC=CCH2 and 2ꢂAr-CH3);
13C NMR (75.4 MHz, CDCl3): d=192.3, 173.1, 142.5, 139.9,
136.6, 136.0, 135.8, 133.7, 129.7, 128.7, 127.8, 125.5, 123.9,
68.9, 59.2, 31.4, 29.9, 19.8, 19.3; IR (neat): n=1743, 1685,
1598, 1580, 1501, 1448, 1362, 1326, 1278, 1248, 1213, 1195,
1176, 1143, 1127, 1100, 1048, 1018 cmꢀ1; MS (70 eV, EI); m/
z (%)=334 (M+, 3.22), 105 (100); HR-MS: m/z=334.1567,
calcd. for C22H22O3 (M+): 334.1569.
Synthesis of 3-Benzoyl-5-(4-methoxyphenyl)-5(E)-
3,4,7,8-tetrahydro-2H-oxocin-2-one (2h)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.5 mg, 0.025 mmol), PPh3
(13.4 mg, 0.050 mmol), K2CO3 (138.5 mg, 1.0 mmol), p-me-
thoxyphenyl iodide (176.1 mg, 0.75 mmol), and 1c (115.3 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2h [eluent: petrole-
um ether (b.p. 30–608C)/ethyl ether=10/1] as a white solid;
yield 116.8 mg (69%); mp 132–1338C (ethyl ether/petroleum
1
ether). H NMR (300 MHz, CDCl3): d=8.00 (d, J=7.8 Hz,
2H, Ar-H), 7.54 (t, J=7.4 Hz, 1H, Ar-H), 7.42 (t, J=7.5 Hz,
2H, Ar-H), 7.28 (d, J=8.7 Hz, 2H, Ar-H), 6.87 (d, J=
8.7 Hz, 2H, Ar-H), 5.96 (t, J=8.0 Hz, 1H, =CH), 4.58 (t, J=
11.4 Hz, 1H, one proton from OCH2), 4.35 (dd, J1 =11.6 Hz,
J2 =4.1 Hz, 1H, O2CCH), 4.15–4.05 (m, 1H, one proton
from OCH2), 3.80 (s, 3H, OMe), 3.72 [t, J=12.3 Hz, 1H,
one proton from C=C(Ar)CH2], 2.95–2.77 [m, 2H, one
proton from C=C(Ar)CH2 and one proton from ArC=
CCH2], 2.30–2.15 (m, 1H, ArC=CCH2); 13C NMR
(75.4 MHz, CDCl3): d=192.2, 173.1, 159.2, 142.0, 135.7,
134.7, 133.7, 128.70, 128.65, 127.6, 125.0, 113.8, 69.0, 59.2,
55.2, 31.3, 29.0; IR (neat): n=1742, 1684, 1600, 1575, 1513,
1462, 1426, 1330, 1293, 1275, 1238, 1205, 1190, 1139, 1057,
1028, 1012 cmꢀ1; MS (70 eV, EI): m/z (%)=336 (M+, 10.39),
77 (100); anal. calcd. for C21H20O4 (%): C 74.98, H 5.99;
found: C 75.02, H 6.04.
Synthesis of 3-Benzoyl-5-(2,3 dihydrobenzo[b]ACTHNUGTRNEUNG[1,4]-
dioxin-6-yl)-5(E)-3,4,7,8-tetrahydro-2H-oxocin-2-one
(2k)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.5 mg, 0.025 mmol), PPh3
(13.4 mg, 0.050 mmol), K2CO3 (138.9 mg, 1.0 mmol), 6-iodo-
1,4-benzodioxane (196.5 mg, 0.75 mmol), and 1c (116.0 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2k [eluent: petrole-
um ether (bp 30–608C)/ethyl ether=10/1] as a white solid;
yield: 121.3 mg (66%); mp 142–1438C (ethyl ether/petrole-
um ether). 1H NMR (300 MHz, CDCl3): d=8.02 (d, J=
7.8 Hz, 2H, Ar-H), 7.55 (t, J=7.4 Hz, 1H, Ar-H), 7.43 (t,
J=7.4 Hz, 2H, Ar-H), 6.93–6.77 (m, 3H, Ar-H), 5.98 (t, J=
8.1 Hz, 1H, =CH), 4.56 (t, J=11.6 Hz, 1H, one proton from
OCH2), 4.37 (dd, J1 =11.6 Hz, J2 =4.1 Hz, 1H, O2CCH), 4.25
(s, 4H, OCH2CH2O), 4.15–4.02 (m, 1H, one proton from
OCH2), 3.70 [t, J=12.5 Hz, 1H, one proton from C=
C(Ar)CH2], 2.93–2.70 [m, 2H, one proton from C=
C(Ar)CH2 and one proton from ArC=CCH2], 2.29–2.15 (m,
1H, one proton from ArC=CCH2); 13C NMR (75.4 MHz,
CDCl3): d=192.2, 173.0, 143.3, 143.2, 141.7, 135.8, 135.7,
Synthesis of 3-Benzoyl-5-(m-tolyl)-5(E)-3,4,7,8-tetra-
hydro-2H-oxocin-2-one (2i)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.5 mg, 0.025 mmol), PPh3
(13.3 mg, 0.050 mmol), K2CO3 (138.4 mg, 1.0 mmol), m-
methylphenyl iodide (163.0 mg, 0.75 mmol), and 1c
(115.6 mg, 0.50 mmol) in 4 mL of CH3CN afforded 2i
[eluent: petroleum ether (bp 30–608C)/ethyl ether=10/1] as
1
an oil; yield: 124.8 mg (78%). H NMR (300 MHz, CDCl3):
d=8.00 (d, J=7.8 Hz, 2H, Ar-H), 7.52 (t, J=7.4 Hz, 1H,
Ar-H), 7.40 (t, J=7.7 Hz, 2H, Ar-H), 7.22 (t, J=7.4 Hz, 1H,
Ar-H), 7.17–7.05 (m, 3H, Ar-H), 5.99 (t, J=8.0 Hz, 1H, = 133.7, 128.71, 128.69, 125.2, 119.5, 117.2, 115.3, 68.9, 64.4,
CH), 4.57 (t, J=11.4 Hz, 1H, one proton from OCH2), 4.35 64.3, 59.2, 31.2, 29.9; IR (neat): n=1742, 1688, 1596, 1579,
1770
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1763 – 1774