2200
X. Wang et al. / Tetrahedron 70 (2014) 2195e2202
123e124 ꢀC. IR (KBr) nmax¼3066, 2968, 2854, 1687, 1667, 1597, 1574,
1447, 1378, 1341, 1251, 1192, 944, 870, 758, 688 cmꢂ1. The ratio of
two diastereomers is 1.3:1. Two diastereomers: 1H NMR (600 MHz,
1573, 1447, 1259, 1170, 1052, 948, 843 cmꢂ1. The ratio of two di-
astereomers is 1:1, Two diastereomers: 1H NMR (600 MHz, CDCl3)
d
8.05 (d, J¼7.6 Hz, 2H), 8.02 (d, J¼7.5 Hz, 2H), 7.63e7.57 (m, 2H),
CDCl3)
d
8.05 (t, J¼8.8 Hz, 4H), 7.88 (dd, J¼12.7, 7.8 Hz, 2H),
7.52e7.46 (m, 4H), 4.71 (t, J¼6.9 Hz, 1H), 4.63 (t, J¼6.9 Hz, 1H),
7.58e7.54 (m, 2H), 7.47e7.42 (m, 4H), 7.37 (dd, J¼17.5, 7.6 Hz, 2H),
2.61e2.43 (m, 2H), 2.17 (s, 3H), 2.13 (s, 3H).13C NMR (150 MHz, CDCl3)
7.29e7.21 (m, 4H), 5.69e5.65 (m, 2H), 2.82e2.73 (m, 2H), 2.47 (s,
d
¼203.9, 203.4, 196.6, 196.4, 135.9, 135.6, 134.0, 129.0, 128.9, 128.9,
3H), 2.43 (s, 3H). 13C NMR (150 MHz, CDCl3)
d¼199.7, 199.5, 196.7,
128.8, 59.3, 59.1, 29.4, 29.1, 27.4, 27.0ppm. LC/MS:m/z¼359 [MþNa]þ.
196.5, 139.5, 136.7, 136.6, 135.8, 135.7, 133.8, 133.7, 132.2, 132.2,
132.0, 132.0, 128.9, 128.9, 128.7, 128.7, 126.1, 56.3, 29.1, 21.2 ppm. LC/
MS: m/z¼511 [MþNa]þ. HR-MS (ESI): m/z¼511.1880, calcd for
4.4.8. 3,5-Bis-(4-chlorobenzoyl)heptane-2,6-dione
(3h). Yield:
82.8 mg (82%) light yellow solid, mp 51e52 ꢀC. IR (KBr) nmax¼3095,
2963, 2839, 1682, 1591, 1490, 1425, 1362, 1323, 1092, 928, 852,
762 cmꢂ1. The ratio of two diastereomers is 1.2:1, Two di-
C
33H28NaO4 [MþNa]þ: 511.1883.
4.4.3. 2-Benzoyl-4-(4-methylbenzoyl)-5-phenyl-1-p-tolylpentane-
1,5-dione (3c).15 Yield: 114.7 mg (94%), light yellow powder. IR
(KBr) nmax¼3062, 2924, 2859, 1692, 1687, 1604, 1447, 1349, 1261,
1181, 949, 831, 796, 688 cmꢂ1. Two diastereomers: 1H NMR
astereomers: 1H NMR (600 MHz, CDCl3)
d
8.04 (d, J¼8.3 Hz, 2H), 7.97
(d, J¼8.4 Hz, 2H), 7.54e7.43 (m, 4H), 4.65 (t, J¼6.8 Hz, 1H), 4.56 (t,
J¼6.8 Hz, 1H), 2.57e2.39 (m, 2H), 2.18 (s, 3H), 2.15 (s, 3H). 13C NMR
(150 MHz, CDCl3)
131.6, 130.4, 130.2, 129.4, 129.4, 128.9, 59.3, 59.1, 29.5, 29.1, 27.3,
d
¼203.2, 195.5, 195.2, 149.4, 140.9, 134.2, 133.8,
(600 MHz, CDCl3)
d
8.11 (t, J¼8.0 Hz, 4H), 8.02 (t, J¼8.7 Hz, 4H),
7.57e7.54 (m, 2H), 7.48e7.44 (m, 4H), 7.27e7.24 (m, 4H), 5.69 (t,
26.8 ppm. LC/MS: m/z¼427 [MþNa]þ.
J¼7.1 Hz, 2H), 2.75e2.70 (m, 2H), 2.38 (d, J¼3.1 Hz, 6H). 13C NMR
(150 MHz, CDCl3)
d¼196.7, 196.2, 196.1, 144.9, 135.6, 135.5, 133.8,
4.4.9. 2-Benzoyl-4-(3-bromobenzoyl)-1-(3-bromophenyl)-5-
phenylpentane-1,5-dione (3i).15 Yield: 100.1 mg (65%), light yellow
powder. IR (KBr) nmax¼2926, 1693, 1639, 1567, 1419, 1385, 1252,
1187, 1153, 1016, 950, 750, 690 cmꢂ1. Two diastereomers: 1H NMR
133.0, 132.9, 129.7, 129.0, 128.9, 128.8, 128.7, 53.9, 29.0, 21.7 ppm.
LC/MS: m/z¼511 [MþNa]þ.
4.4.4. 2-Benzoyl-4-(2-methoxybenzoyl)-1-(2-methoxyphenyl)-5-
phenylpentane-1,5-dione (3d). Yield: 89.7 mg (69%), yellow powder,
mp 148e150 ꢀC. IR (KBr) nmax¼3065, 2975, 2842, 1685, 1663, 1596,
1482, 1437, 1288, 1254, 1183, 1157, 1049, 951, 839 cmꢂ1. The ratio of
two diastereomers is 2.9:1, Two diastereomers: 1H NMR (600 MHz,
(600 MHz, CDCl3)
d
8.25 (d, J¼1.3 Hz, 2H), 8.13 (t, J¼7.9 Hz, 4H), 8.07
(t, J¼9.0 Hz, 2H), 7.71 (d, J¼7.9 Hz, 2H), 7.61 (t, J¼7.2 Hz, 2H),
7.52e7.48 (m, 4H), 7.38e7.35 (m, 2H), 5.65 (t, J¼7.0 Hz, 2H),
2.79e2.69 (m, 2H). 13C NMR (150 MHz, CDCl3)
d
¼196.1, 196.1, 195.2,
195.2, 137.1, 137.0, 136.8, 135.1, 135.1, 134.1, 131.7, 130.6, 129.1, 128.8,
CDCl3)
d
8.42 (d, J¼7.1 Hz, 3H), 8.12 (d, J¼7.4 Hz, 1H), 8.04 (dd, J¼7.8,
128.8, 127.3, 123.5, 54.0, 28.6 ppm. LC/MS: m/z¼641[MþNa]þ.
1.7 Hz, 1H), 7.75 (dd, J¼7.8, 1.7 Hz, 1H), 7.65e7.52 (m, 5H), 7.48e7.38
(m, 3H), 7.01e6.59 (m, 2H), 6.86 (d, J¼8.4 Hz, 1H), 6.78 (d, J¼8.3 Hz,
1H), 5.82e5.76 (m, 2H), 3.56 (s, 2H), 3.27 (s, 4H), 2.69e2.55 (m, 2H).
4.4.10. 2-Benzoyl-4-(3-chlorobenzoyl)-1-(3-chlorophenyl)-5-
phenylpentane-1,5-dione (3j). Yield: 99 mg (75%), light yellow
powder, mp 116e117 ꢀC. IR (KBr) nmax¼3067, 2933,1692,1673,1594,
1570, 1447, 1349, 1073, 948, 890, 779, 737, 686 cmꢂ1. Two di-
13C NMR (150 MHz, CDCl3)
d
¼197.6, 196.7, 158.6, 135.5, 134.4, 133.3,
131.2, 129.2, 128.8, 126.1, 120.8, 111.5, 58.7, 54.7, 28.6 ppm. LC/MS:
m/z¼543 [MþNa]þ. HR-MS (ESI): m/z¼543.1778, calcd for
astereomers: 1H NMR (600 MHz, CDCl3)
d
8.12 (t, J¼7.4 Hz, 4H),
C
33H28NaO6 [MþNa]þ: 543.1787.
8.10e8.07 (m, 2H), 8.02 (t, J¼7.8 Hz, 2H), 7.61 (t, J¼7.4 Hz, 2H),
7.58e7.54 (m, 2H), 7.51 (t, J¼7.7 Hz, 4H), 7.43 (t, J¼7.9 Hz, 2H), 5.64
(t, J¼7.0 Hz, 2H), 2.78e2.67 (m, 2H). 13C NMR (150 MHz, CDCl3)
4.4.5. 2-Benzoyl-4-(3-methoxybenzoyl)-1-(3-methoxyphenyl)-5-
phenylpentane-1,5-dione (3e). Yield: 119.6 mg (92%), yellow pow-
der, mp 52e54 ꢀC. IR (KBr) nmax¼3065, 2936, 2836,1695,1670,1597,
1488, 1429, 1269, 1163, 1042, 997, 875, 783, 689 cmꢂ1. The ratio of
two diastereomers is 1:1, Two diastereomers: 1H NMR (600 MHz,
d
¼196.2, 196.2, 195.4, 195.3, 137.0, 136.9, 135.5, 135.2, 135.1, 134.1,
133.9, 130.4, 129.1, 128.8, 128.8, 126.9, 54.0, 28.7 ppm. LC/MS: m/
z¼551 [MþNa]þ. HR-MS (ESI): m/z¼551.0787, calcd for
C
31H22Cl2NaO4 [MþNa]þ: 551.0794.
CDCl3)
d
8.14 (dd, J¼12.1, 7.7 Hz, 4H), 7.75 (t, J¼8.1 Hz, 2H), 7.71 (s,
1H), 7.67 (s, 1H), 7.58 (dd, J¼12.6, 7.2 Hz, 2H), 7.49 (dd, J¼14.7,
7.3 Hz, 4H), 7.41e7.37 (m, 2H), 7.16e7.11 (m, 2H), 5.72 (t, J¼7.0 Hz,
2H), 3.84 (d, J¼12.1 Hz, 6H), 2.81e2.74 (m, 2H). 13C NMR (150 MHz,
4.4.11. 2-Benzoyl-4-(3-fluorobenzoyl)-1-(3-fluorophenyl)-5-
phenylpentane-1,5-dione (3k). Yield: 75.6 mg (61%), light yellow
powder, mp 141e142 ꢀC. IR (KBr) nmax¼3071, 2907, 2849, 1692,
1672, 1588, 1445, 1265, 1186, 1001, 954, 884, 749, 688 cmꢂ1. Two
CDCl3)
d¼196.5, 196.4, 196.4, 196.3, 160.0, 136.7, 135.4, 133.9, 130.0,
129.0, 128.9, 128.8, 128.7, 121.4, 120.9, 120.8, 112.5, 112.5, 55.4, 55.4,
54.1, 28.9 ppm. LC/MS: m/z¼543 [MþNa]þ. HR-MS (ESI): m/
z¼543.1778, calcd for C33H28NaO6 [MþNa]þ: 543.1800.
diastereomers: 1H NMR (600 MHz, CDCl3)
d 8.16e8.10 (m, 4H), 7.93
(t, J¼6.6 Hz, 2H), 7.81 (dd, J¼8.9, 1.5 Hz, 2H), 7.61 (t, J¼7.4 Hz, 2H),
7.52e7.46 (m, 6H), 7.31e7.28 (m, 2H), 5.66 (t, J¼7.0 Hz, 2H),
2.79e2.69 (m, 2H). 13C NMR (150 MHz, CDCl3)
d¼196.2,195.4,163.8,
4.4.6. 2-Benzoyl-4-(4-methoxybenzoyl)-1-(4-methoxyphenyl)-5-
phenylpentane-1,5-dione (3f).15 Yield: 104 mg (80%), light yellow
powder. IR (KBr) nmax¼3059, 3011, 2932, 2843, 1689, 1664, 1549,
1510, 1421, 1259, 1170, 1026, 949 cmꢂ1. The ratio of two di-
astereomers is 1:1, Two diastereomers: 1H NMR (600 MHz, CDCl3)
162.2, 137.5, 137.5, 137.4, 135.2, 135.1, 134.1, 130.8, 130.7, 129.1, 128.8,
124.6, 121.1, 121.0, 115.5, 115.4, 54.1, 28.8 ppm. LC/MS: m/z¼519
[MþNa]þ. HR-MS (ESI): m/z¼519.1378, calcd for C31H22F2NaO4
[MþNa]þ: 519.1399.
d
8.21 (d, J¼8.9 Hz, 2H), 8.13 (t, J¼9.0 Hz, 4H), 8.07 (d, J¼7.5 Hz, 2H),
4.4.12. 2,4-Bis-(4-methylbenzoyl)-1,5-dip-tolylpentane-1,5-dione
(3l).10d Yield: 94.2 mg (73%), yellow powder. IR (KBr) nmax¼3031,
2963, 2856, 1688, 1668, 1606, 1570, 1411, 1382, 1349, 1263, 1182,
7.60e7.53 (m, 2H), 7.49e7.43 (m, 4H), 6.99 (d, J¼8.8 Hz, 2H), 6.95 (d,
J¼8.9 Hz, 2H), 5.68 (t, J¼7.1 Hz, 2H), 3.87 (s, 3H), 3.85 (s, 3H),
2.78e2.69 (m, 2H). 13C NMR (150 MHz, CDCl3)
d
¼196.8, 195.2, 195.1,
1096, 948, 806 cmꢂ1. 1H NMR (600 MHz, CDCl3)
d
7.95 (d, J¼8.2 Hz,
164.1,164.0,135.7,135.5,133.7,133.6,131.4,131.2,129.0,128.9,128.8,
128.6, 128.5, 128.3, 114.2, 114.1, 55.5, 53.8, 29.1 ppm. LC/MS: m/
z¼543 [MþNa]þ.
7H), 7.21e7.17 (m, 9H), 5.59 (t, J¼7.1 Hz, 2H), 2.63 (t, J¼7.0 Hz, 2H),
2.32 (s, 12H). 13C NMR (150 MHz, CDCl3)
d
¼196.3, 144.7, 133.1, 129.7,
128.9, 53.9, 29.1, 21.7 ppm. LC/MS: m/z¼539 [MþNa]þ.
4.4.7. 3,5-Dibenzoylheptane-2,6-dione (3g).15 Yield: 79.8 mg (95%),
light yellow solid. IR (KBr) nmax¼3063, 2935, 2840, 1690, 1663, 1595,
4.4.13. 2,4-Bis-(2-methylbenzoyl)-1,5-dio-tolylpentane-1,5-dione
(3m). Yield: 120 mg (93%), yellow powder, mp 73e74 ꢀC. IR (KBr)