3832
I. Ullah et al. / Tetrahedron 66 (2010) 3824–3835
CH2), 2.92 (t, 2H, 3J¼4.8 Hz, CH2), 3.87 (s, 3H, OCH3), 6.86 (d, 2H,
3J¼7.9 Hz, HAr), 7.11–7.23 (m, 7H, HAr), 11.24 (s, 1H, OH); 13C NMR
654, 565 (m); GC–MS (EI, 70 eV): m/z (%)¼353 (19), 352 (Mþ, 88),
320 (88), 305 (65), 292 (100), 263 (48), 249 (61), 235 (35), 203 (32),
179 (25), 165 (10), 152 (11), 129 (31); HRMS (EI): calcd for C23H28O3
[M]þ: 352.20330; found: 352.20362.
(75 MHz, CDCl3):
d
¼14.0, 18.1, 20.9 (CH3), 22.4, 29.1, 33.6, 35.1, 35.3
(CH2), 52.0 (OCH3), 110.4 (CAr), 125.7 (CHAr), 125.9 (CAr),128.2 (2CHAr),
128.4 (2CHAr), 128.7 (2CHAr), 129.6 (2CHAr), 135.1, 135.8, 138.9, 141.1,
142.0, 142.6, 159.0 (CAr), 172.8 (C]O); IR (KBr, cmꢀ1):
¼ 3024ðwÞ;
3.4.29. Methyl
5-(but-3-enyl)-40-butyl-4-hydroxy-2,6-dimethylbi-
~
n
2951 (m), 2859 (w), 1707, 1650, 1599, 1512, 1452, 1405, 1354,1293 (m),
1220 (s), 1160, 1083, 1029, 949, 870, 804, 743 (m), 696 (s), 614, 567
(m); EIMS (EI, 70 eV): m/z (%)¼416 (Mþ, 24), 385 (16), 325 (42), 283
(28), 252 (35), 251 (100), 237 (10), 180 (19), 165 (11), 152 (12), 91 (8);
HRMS (EI): calcd for C28H33O3 [MþH]þ: 417.24242; found: 417.24261.
phenyl-3-carboxylate (6ac). Starting with 1,3-bis(silyl enol ether) 5i
(500 mg, 1.58 mmol), 3-(4-butylphenyl)-4-(trimethylsilyloxy)pent-
3-en-2-one 4d (481 mg,1.58 mmol), and TiCl4 (0.17 mL,1.58 mmol),
6ac was obtained as a yellowish solid (306 mg, 53%), mp¼76–78 ꢁC.
1H NMR (300 MHz, CDCl3):
d
¼0.79 (t, 3H, 3J¼7.2 Hz, CH3), 1.20
(sextet, 2H, 3J¼7.3 Hz, CH2), 1.44 (quintet, 2H, 3J¼7.6 Hz, CH2), 1.76
(s, 3H, CH3), 1.95 (s, 3H, CH3), 2.10–2.13 (m, 2H, CH2), 2.46 (t, 2H,
3J¼7.4 Hz, CH2), 2.62 (t, 2H, 3J¼7.6 Hz, CH2), 3.75 (s, 3H, OCH3),
4.77–4.92 (m, 2H, ]CH2), 5.69–5.83 (m, 1H, ]CH), 6.78 (d, 2H,
3J¼8.0 Hz, HAr), 7.02 (d, 2H, 3J¼8.0 Hz, HAr), 11.07 (s, 1H, OH); 13C
3.4.26. Methyl 40-butyl-5-hexyl-4-hydroxy-2,6-dimethylbiphenyl-3-
carboxylate (6z). Starting with 1,3-bis(silyl enol ether) 5h (600 mg,
1.74 mmol), 3-(4-butylphenyl)-4-(trimethylsilyloxy)pent-3-en-2-
one 4d (530 mg, 1.74 mmol), and TiCl4 (0.19 mL, 1.74 mmol), 6z was
obtained as a yellowish solid (331 mg, 48%), mp¼84–85 ꢁC. 1H NMR
NMR (75 MHz, CDCl3):
d
¼13.9, 18.3, 20.9 (CH3), 22.4, 26.2, 33.0,
(300 MHz, CDCl3):
d
¼0.71 (t, 3H, 3J¼7.2 Hz, CH3), 0.78 (t, 3H,
33.6, 35.3 (CH2), 52.0 (OCH3), 110.4 (CAr), 114.4 (]CH2), 126.0 (CAr),
3J¼7.3 Hz, CH3), 1.09–1.59 (m, 12H, 6CH2), 1.76 (s, 3H, CH3), 1.95 (s,
3H, CH3), 2.47–2.52 (m, 4H, 2CH2), 3.75 (s, 3H, OCH3), 6.78 (d, 2H,
3J¼7.9 Hz, HAr), 7.02 (d, 2H, 3J¼7.9 Hz, HAr), 11.04 (s, 1H, OH); 13C
128.4 (2CHAr), 129.6 (2CHAr), 135.1, 135.7 (CAr), 138.8 (]CH), 139.0,
141.1, 142.1, 158.9 (CAr), 172.8 (C]O); IR (KBr, cmꢀ1):
¼ 2954ðmÞ;
~
n
2858, 2667, 1786 (w), 1710, 1655, 1606 (m), 1511 (w), 1438, 1377,
1324, 1286 (m), 1216 (s), 1157, 1058, 991, 906, 807 (m), 751, 700 (s),
634 (w), 576 (m); GC–MS (EI, 70 eV): m/z (%)¼367 (33), 366 (Mþ,
100), 335 (25), 333 (12), 305 (9), 293 (24), 277 (11), 249 (11), 235
(29), 203 (10), 179 (9), 165 (9), 152 (6), 115 (9); HRMS (EI): calcd for
C24H30O3 [M]þ: 366.21895; found: 366.21880.
NMR (75 MHz, CDCl3):
30.2, 30.9, 32.9, 34.7, 36.5 (CH2), 53.0 (OCH3), 111.5, 128.3 (CAr),
d¼15.2, 15.3, 19.4, 22.1 (CH3), 23.6, 23.8, 27.9,
129.6 (2CHAr), 130.8 (2CHAr), 135.2, 136.3, 140.3, 142.2, 143.0, 160.0
(CAr), 174.0 (C]O); IR (KBr, cmꢀ1):
n
¼ 2953; 2855 (m), 1933 (w),
~
1703 (m),1654 (s),1593 (m),1512 (w),1438,1377,1325 (m),1213 (s),
1141, 1057, 987 (m), 901 (w), 840, 752, 696, 651, 578 (m); MS (EI,
70 eV): m/z (%)¼396 (Mþ, 42), 365 (25), 335 (35), 294 (100), 293
(54), 251 (18), 237 (29), 209 (19), 165 (11); HRMS (EI): calcd for
C26H37O3 [MþH]þ: 397.27372; found: 397.27411.
3.4.30. Methyl 40-butyl-5-chloro-4-hydroxy-2,6-dimethylbiphenyl-3-
carboxylate (6ad). Starting with 1,3-bis(silyl enol ether) 5j (600 mg,
2.06 mmol), 3-(4-butylphenyl)-4-(trimethylsilyloxy)pent-3-en-2-
one 4d (627 mg, 2.06 mmol), and TiCl4 (0.22 mL, 2.06 mmol), 6ad
was obtained as a light yellowish solid (250 mg, 35%), mp¼71–73 ꢁC.
3.4.27. Methyl 40-butyl-4-hydroxy-2,6-dimethyl-5-nonylbiphenyl-3-
carboxylate (6aa). Starting with 1,3-bis(silylenol ether) 5k (600 mg,
1.55 mmol), 3-(4-butylphenyl)-4-(trimethylsilyloxy)pent-3-en-2-
one 4d (472 mg,1.55 mmol), and TiCl4 (0.17 mL,1.55 mmol), 6aa was
obtained as a yellowish solid (285 mg, 42%), mp¼66–68 ꢁC. 1H NMR
1H NMR (300 MHz, CDCl3):
d
¼0.96 (t, 3H, 3J¼7.2 Hz, CH3), 1.40
(sextet, 2H, 3J¼7.3 Hz, CH2),1.64 (quintet, 2H, 3J¼7.5 Hz, CH2), 2.09 (s,
3H, CH3), 2.17 (s, 3H, CH3), 2.65 (t, 2H, 3J¼7.4 Hz, CH2), 3.98 (s, 1H,
OCH3), 6.97 (d, 2H, 3J¼7.8 Hz, HAr), 7.24 (d, 2H, 3J¼7.8 Hz, HAr), 11.37
(300 MHz, CDCl3):
d
¼0.69 (t, 3H, 3J¼6.7 Hz, CH3), 0.78 (t, 3H,
(s,1H, OH); 13C NMR (62 MHz, CDCl3):
d¼13.9,19.6, 20.7 (CH3), 22.4,
3J¼7.2 Hz, CH3),1.09–1.58 (m,18H, 9CH2),1.76(s, 3H, CH3),1.95 (s, 3H,
CH3), 2.45–2.53 (m, 4H, 2CH2), 3.75 (s, 3H, OCH3), 6.78 (d, 2H,
3J¼8.0 Hz, HAr), 7.03 (d, 2H, 3J¼8.0 Hz, HAr), 11.03 (s, 1H, OH); 13C
33.5, 35.3 (CH2), 52.4 (OCH3), 112.1, 120.2 (CAr), 128.4 (2CHAr), 129.4
(2CHAr), 135.6, 139.5, 137.7, 141.6, 142.1, 156.0 (CAr), 172.0 (C]O); IR
(KBr, cmꢀ1):
¼ 3412ðwÞ; 2955 (m), 2858, 2671, 2551, 1807 (w),
~
n
NMR (75 MHz, CDCl3):
27.8, 30.2, 30.5, 30.7, 30.8, 31.1, 34.8, 36.6 (CH2), 53.1 (OCH3), 111.5,
d¼15.2, 15.3, 19.4, 22.1 (CH3), 22.8, 23.6, 23.7,
1706, 1666, 1605 (m), 1553 (w), 1416, 1353, 1285 (m), 1217 (s), 1157,
1102, 1001, 899, 805, 750, 697, 571 (m); GC–MS (EI, 70 eV): m/z
(%)¼348 (Mþ, 37Cl, 7), 346 (Mþ, 35Cl, 23), 316 (38), 315 (24), 314 (100),
271 (17), 243 (6), 237 (10), 166 (3), 165 (9), 152 (3); HRMS (EI): calcd
for C20H23ClO3 [M]þ: 346.13302; found: 346.13295.
128.2 (CAr), 129.6 (2CHAr), 130.8 (2CHAr), 136.2, 136.5, 140.2, 142.2,
143.0, 160.0 (CAr),174.0 (C]O); IR (KBr, cmꢀ1):
n
¼ 2953; 2853 (m),
~
1731 (w), 1654 (s), 1593 (m), 1512 (w), 1438 (m), 1325,1212 (s), 1140,
1058, 987 (m), 887 (w), 807, 752, 651, 578 (m); GC–MS (EI, 70 eV):
m/z (%)¼438 (Mþ, 38), 406 (22), 391 (30), 389 (32), 349 (56), 335 (51),
295 (20), 294 (100), 293 (50), 251 (14), 237 (22), 209 (15), 165 (15);
HRMS (EI): calcd for C29H42O3 [M]þ: 438.64583; found: 438.64927.
3.4.31. 40-Ethyl 3-methyl 4-hydroxy-2,6-dimethylbiphenyl-3,40-di-
carboxylate (6ae). Starting with 1,3-bis(silyl enol ether) 5a (500 mg,
1.91 mmol),
ethyl
4-(4-oxo-2-(trimethylsilyloxy)pent-2-en-3-
yl)benzoate 4e (612 mg,1.91 mmol), and TiCl4 (0.21 mL,1.91 mmol),
3.4.28. Methyl 5-allyl-40-butyl-4-hydroxy-2,6-dimethylbiphenyl-3-
carboxylate (6ab). Starting with 1,3-bis(silyl enol ether) 5l (600 mg,
1.99 mmol), 3-(4-butylphenyl)-4-(trimethylsilyloxy)pent-3-en-2-
one 4d (606 mg, 1.99 mmol), and TiCl4 (0.21 mL, 1.99 mmol), 6ab
was obtained as a yellowish solid (386 mg, 55%), mp¼74–76 ꢁC. 1H
6ae was obtained as colorless solid (376 mg, 60%), mp¼86–87 ꢁC. 1H
NMR (300 MHz, CDCl3):
d
¼1.42 (t, 3H, 3J¼7.0 Hz, CH3), 1.93 (s, 3H,
CH3), 2.17 (s, 3H, CH3), 3.95 (s, 3H, OCH3), 4.41 (q, 2H, 3J¼7.0 Hz,
OCH2), 6.78 (s, 1H, HAr), 7.18 (d, 2H, 3J¼8.5 Hz, HAr), 8.12 (d, 2H,
3J¼8.5 Hz, HAr), 11.05 (s, 1H, OH); 13C NMR (75 MHz, CDCl3):
¼14.3,
d
NMR (300 MHz, CDCl3):
d
¼0.78 (t, 3H, 3J¼7.2 Hz, CH3), 1.18 (sextet,
20.7, 21.7 (CH3), 52.0 (OCH3), 61.0 (OCH2), 110.9 (CAr), 116.4 (CHAr),
2H, 3J¼7.3 Hz, CH2), 1.45 (quintet, 2H, 3J¼7.6 Hz, CH2), 1.75 (s, 3H,
CH3), 1.95 (s, 3H, CH3), 2.47 (t, 2H, 3J¼7.4 Hz, CH2), 3.32 (d, 2H,
3J¼5.7 Hz, CH2), 3.75 (s, 3H, OCH3), 4.76–4.98 (m, 2H, ]CH2), 5.72–
5.85 (m, 1H, ]CH), 6.78 (d, 2H, 3J¼8.1 Hz, HAr), 7.03 (d, 2H,
129.1 (CAr), 129.7 (2CHAr), 129.8 (2CHAr), 134.0, 138.1, 143.3, 145.8,
161.2 (CAr), 166.4, 172.0 (C]O); IR (KBr, cmꢀ1):
n
¼ 2981; 2954,
~
1712 (w), 1659, 1607, 1440, 1351, 1321 (m), 1269 (s), 1175 (m), 1099
(s), 993, 907, 804 (m), 727 (s), 647 (m), 564 (w); GC–MS (EI, 70 eV):
m/z (%)¼328 (Mþ, 25), 297 (23), 296 (100), 268 (11), 165 (11), 152
(11); HRMS (EI): calcd for C19H20O5 [M]þ: 328.13053; found:
328.13047.
3J¼8.1 Hz, HAr), 11.09 (s, 1H, OH); 13C NMR (75 MHz, CDCl3):
¼15.1,
d
19.4, 22.1 (CH3), 23.5, 30.8, 34.7, 36.5 (CH2), 53.2 (OCH3), 111.7 (CAr),
115.7 (]CH2), 124.8 (CAr), 129.6 (2CHAr), 130.8 (2CHAr), 135.2, 136.4
(CAr), 137.0 (]CH), 140.0, 142.3, 143.8, 159.9 (CAr), 173.9 (C]O); IR
~
(KBr, cmꢀ1):
n
¼ 2955; 2926 (m), 2856 (w), 1656, 1595 (m), 1512
3.4.32. Diethyl 4-hydroxy-2,6-dimethylbiphenyl-3,40-dicarboxylate
(6af). Starting with 1,3-bis(silyl enol ether) 5b (500 mg,1.82 mmol),
(w), 1438, 1325, 1287 (m), 1219 (s), 1139, 1059, 993, 911, 833, 750,