Li et al.
JOCArticle
61.0, 55.0, 52.3, 43.3, 41.5, 34.9, 32.0, 13.8, 13.6; FTIR (film)
2976, 2934, 2835, 1730, 1607, 1580, 1508, 1462, 1444, 1366, 1332,
6.58 (d, J = 2.4, 1H), 6.50 (dd, J = 8.4, 2.4, 1H), 4.07 (q, J = 7.2,
1H), 4.06 (q, J = 7.2, 1H), 3.76 (dq, J = 10.8, 7.2, 1H), 3.80 (s,
3H), 3.73 (s, 3H), 3.38 (dq, J = 10.8, 7.2, 1H), 3.28 (d, J = 16.2,
1H), 3.09 (d, J = 16.2, 1H), 2.90 (d, J = 14.1, 1H), 2.45 (d, J =
14.1, 1H), 1.69 (s, 3H), 1.20 (t, J = 7.2, 3H), 1.00 (t, J = 7.2, 3H);
13C NMR (75 MHz, CDCl3) δ 171.8, 170.6, 148.0, 146.9, 141.8,
141.7, 134.2, 128.7, 128.0, 126.4, 126.2, 119.7, 111.3, 110.2, 61.3,
61.0, 55.7, 55.6, 52.4, 43.2, 41.9, 34.9, 32.0, 13.9, 13.8; FTIR
(film) 2975, 2934, 2834, 1729, 1604, 1588, 1511, 1463, 1444,
1408, 1366, 1332, 1251, 1236, 1211, 1183, 1165, 1146, 1124, 1093,
1051, 1026, 947, 912, 858, 808, 768, 730, 650 cm-1; HRMS
(TOF-QII) m/z calcd for C25H30O6Na [M þ Na]þ 449.1940,
found 449.1928.
1247, 1215, 1127, 1091, 1030, 860, 810, 830, 768, 732 cm-1
;
HRMS (TOF-QII) m/z calcd for C24H28O5Na [M þ Na]þ
419.1835, found 419.1820.
Compound 5: colorless oil; 81% yield; H NMR (300 MHz,
1
CDCl3) δ 7.26-7.15 (m, 2H), 7.03 (d, J = 9.0, 2H), 6.99-6.78
(m, 2H), 6.75 (d, J = 9.0, 2H), 4.16-4.06 (m, 4H), 3.78 (s, 3H),
3.24 (d, J = 13.8, 1H), 3.18 (d, J = 13.8, 1H), 2.51 (dt, J = 12.9,
4.2, 1H), 1.93 (dt, J = 12.9, 4.2, 1H), 1.68 (dt, J = 13.8, 4.5, 1H),
1.61 (s, 3H), 1.52 (dt, J = 13.8, 4.5, 1H), 1.21 (t, J = 7.2, 3H),
1.18 (t, J = 7.2, 3H); 13C NMR (75 MHz, CDCl3) δ 171.4, 171.2,
157.9, 142.8, 136.8, 136.1, 129.9, 128.0, 127.7, 126.8, 120.4,
112.9, 61.1, 61.0, 58.8, 55.3, 44.2, 37.6, 33.2, 27.1, 26.9, 14.1,
14.0; FTIR (film) 2977, 2936, 1729, 1606, 1510, 1490, 1455, 1368,
1286, 1243, 1219, 1180, 1094, 1032, 914, 862, 829, 740, 702, 623
cm-1; HRMS (TOF-QII) m/z calcd for C25H31O5 [M þ H]þ
411.2166, found 411.2151.
1
Compound 10: 81% yield; H NMR (300 MHz, CDCl3) δ
7.23-7.11 (m, 5H), 6.76 (dd, J = 8.7, 2.1, 1H), 6.71 (d, J = 8.7,
1H), 4.16 (q, J = 7.2, 1H), 4.15 (q, J = 7.2, 1H), 3.86 (dq, J =
10.8, 7.2, 1H), 3.83 (s, 3H), 3.50 (dq, J = 10.8, 7.2, 1H), 3.29 (d,
J = 16.2, 1H), 3.11 (d, J = 16.2, 1H), 2.84 (d, J = 14.4, 1H), 2.47
(d, J = 14.4, 1H), 1.67 (s, 3H), 1.21 (t, J = 7.2, 3H), 1.05 (t, J =
7.2, 3H); 13C NMR (75 MHz, CDCl3) δ 171.7, 170.5, 152.9,
142.4, 141.2, 134.1, 129.1, 128.9, 128.0, 127.0, 126.7, 126.5,
121.7, 111.0, 61.5, 61.2, 56.0, 52.4, 43.2, 41.7, 34.9, 31.9, 13.9,
13.6; FTIR (film) 2977, 1782, 1729, 1602, 1497, 1462, 1443, 1393,
1366, 1332, 1292, 1254, 1220, 1182, 1126, 1095, 1066, 1023, 862,
813, 769, 725, 708, 621 cm-1; HRMS (TOF-QII) m/z calcd for
C24H27ClO5Na [M þ Na]þ 453.1445, found 453.1420.
1
Compound 6: colorless oil; 72% yield; H NMR (300 MHz,
CDCl3) δ 7.26-7.17 (m, 2H), 7.02 (d, J = 8.7, 2H), 7.00-6.77
(m, 2H), 6.75 (d, J = 8.7, 2H), 4.14-4.05 (m, 4H), 3.77 (s, 3H),
3.14 (d, J = 13.8, 1H), 3.09 (d, J = 13.8, 1H), 2.38 (dt, J = 12.0,
4.5, 1H), 1.92 (dt, J = 12.0, 4.5, 1H), 1.74-1.68 (m, 2H), 1.59 (s,
3H), 1.16 (t, J = 7.2, 3H), 1.15 (t, J = 7.2, 3H), 1.09-0.95 (m,
2H); 13C NMR (75 MHz, CDCl3) δ 171.3, 171.2, 156.9, 142.9,
137.2, 136.2, 129.8, 128.1, 127.5, 126.9, 120.3, 112.8, 61.1, 61.0,
58.8, 55.4, 44.5, 39.8, 37.7, 32.2, 27.0, 19.5, 14.0 (2C); FTIR (film)
2960, 1730, 1597, 1510, 1489, 1462, 1369, 1294, 1244, 1213, 1181,
1096, 1032, 925, 830, 701, 618 cm-1; HRMS (TOF-QII) m/z calcd
for C26H33O5 [M þ H]þ 425.2323, found 425.2303.
Compound 11: colorless oil; 88% yield; 1H NMR (300 MHz,
CDCl3) δ 7.32 (d, J = 2.4, 1H), 7.23-7.10 (m, 4H), 6.78 (dd, J =
8.7, 2.4, 1H), 6.68 (d, J = 8.7, 1H), 4.16 (q, J = 7.2, 1H), 4.15 (q,
J = 7.2, 1H), 3.90 (dq, J = 10.8, 7.2, 1H), 3.82 (s, 3H), 3.52 (dq,
J = 10.8, 7.2, 1H), 3.30 (d, J = 16.2, 1H), 3.10 (d, J = 16.2, 1H),
2.83 (d, J = 14.4, 1H), 2.47 (d, J = 14.4, 1H), 1.66 (s, 3H), 1.21
(t, J = 7.2, 3H), 1.05 (t, J = 7.2, 3H); 13C NMR (75 MHz,
CDCl3) δ 171.7, 170.5, 153.8, 142.9, 141.2, 134.1, 132.1, 129.0,
128.0, 127.9, 126.7, 126.5, 111.0, 110.9, 61.5, 61.3, 56.2, 52.4,
43.3, 41.6, 34.9, 32.0, 13.9, 13.7; FTIR (film) 2977, 1730, 1600,
1493, 1462, 1443, 1390, 1366, 1332, 1256, 1220, 1182, 1126, 1095,
1054, 1020, 861, 812, 768 cm-1; HRMS (TOF-QII) m/z calcd for
C24H27BrO5Na [M þ Na]þ 497.0940, found 497.0934.
1
Compound 7: colorless oil; 78% yield; H NMR (300 MHz,
CDCl3, 2:1 mixture of conformers (see below)); major confor-
mer: δ 7.83-7.32 (m, 4H), 7.13 (dd, J = 6.9, 1.5, 1H), 7.10 (dd,
J = 6.9, 1.5, 1H), 6.98 (d, J = 8.7, 2H), 6.73 (d, J = 8.7, 2H),
4.18 (q, J = 7.2, 2H), 3.93 (dq, J = 10.8, 7.2, 1H), 3.75 (s, 3H),
3.65 (dq, J = 10.8, 7.2, 1H), 3.45 (s, 2H), 2.70 (d, J = 14.4, 1H),
2.61 (d, J = 14.4, 1H), 1.90 (s, 3H), 1.24 (t, J = 7.2, 3H), 1.05 (t,
J = 7.2, 3H); 13C NMR (75 MHz, CDCl3) δ 171.7, 170.7, 157.4,
142.3, 136.2, 134.0, 132.5, 131.3, 128.8, 128.1, 128.0, 127.9,
127.8, 124.6, 124.2, 113.4, 61.4, 61.3, 55.2, 51.5, 48.3, 42.3,
36.9, 29.7, 14.0, 13.7; minor conformer: δ 7.83-7.32 (m, 4H),
7.30 (dd, J = 7.8, 1.0, 1H), 7.27 (dd, J = 7.8, 1.0, 1H), 7.13-7.02
(m, 2H), 6.79-6.74 (m, 2H), 4.10 (q, J = 7.2, 2H), 4.05-3.76 (m,
2H), 3.73 (s, 3H), 3.26 (br s, 2H), 3.13 (d, J = 14.7, 1H), 2.51 (d,
J = 14.7, 1H), 1.78 (s, 3H), 1.18 (t, J = 7.2, 3H), 1.14 (t, J = 7.2,
3H); 13C NMR (75 MHz, CDCl3) δ 171.9, 171.2, 157.7, 133.4,
132.6, 132.4, 127.8, 127.1, 127.0, 125.7, 125.6, 125.3, 113.2, 61.5,
53.4, 42.6, 42.5, 13.9 (8 C hidden or accidentally isochronous
with major conformer); FTIR (film) 2979, 2339, 1731, 1607,
Compound 12: colorless oil; 67% yield; 1H NMR (300 MHz,
CDCl3) δ 7.23-7.18 (m, 4H), 6.22 (s, 2H), 4.15 (q, J = 7.2, 1H),
4.14 (q, J = 7.2, 1H), 3.89-3.81 (m, 1H), 3.79 (s, 3H), 3.70 (s,
3H), 3.43 (dq, J = 10.8, 7.2, 1H), 3.30 (d, J = 16.2, 1H), 3.07 (d,
J = 16.2, 1H), 2.90 (dd, J = 14.4, 1.2, 1H), 2.43 (d, J = 14.4,
1H), 1.71 (s, 3H), 1.21 (t, J = 7.2, 3H), 1.00 (t, J = 7.2, 3H); 13C
NMR (75 MHz, CDCl3) δ 171.9, 170.6, 152.2, 144.9, 141.5,
135.8, 134.3, 128.9, 128.2, 126.6, 126.3, 105.2, 61.5, 61.2, 60.6,
55.9, 52.4, 43.2, 42.5, 35.0, 32.0, 14.0, 13.7; FTIR (film) 2983,
1731, 1587, 1508, 1456, 1413, 1256, 1126, 1010, 748, 620 cm-1
;
1509, 1463, 1367, 1296, 1248, 1182, 1102, 1034, 832, 732 cm-1
;
HRMS (TOF-QII) m/z calcd for C26H32O7Na [M þ Na]þ
HRMS (TOF-QII) m/z calcd for C28H30O5Na [M þ Na]þ
479.2040, found 479.2045.
Compound 13: colorless oil; 87% yield; 1H NMR (300 MHz,
CDCl3) δ 7.22-7.19 (m, 4H), 6.23 (s, 2H), 5.34 (br s, 1H, OH),
4.15 (q, J = 7.2, 1H), 4.14 (q, J = 7.2, 1H), 3.89-3.82 (m, 1H),
3.73 (s, 6H), 3.49 (dq, J = 10.8, 7.2, 1H), 3.27 (d, J = 15.9, 1H),
3.08 (d, J = 15.9, 1H), 2.91 (d, J = 14.4, 1H), 2.42 (d, J = 14.4,
469.1985, found 469.1979.
Compound 8: colorless oil; 90% yield; H NMR (300 MHz,
1
CDCl3) δ 7.23-7.13 (m, 4H), 6.90 (d, J = 2.1, 1H), 6.71 (dd, J =
8.7, 2.1, 1H), 6.62 (d, J = 8.7, 1H), 4.17 (q, J = 7.0, 1H), 4.16 (q,
J = 7.0, 1H), 3.84 (dq, J = 10.8, 7.2, 1H), 3.77 (s, 3H), 3.48 (dq,
J = 10.8, 7.2, 1H), 3.31 (d, J = 16.2, 1H), 3.13 (d, J = 16.2, 1H),
2.88 (d, J = 14.4, 1H), 2.48 (d, J = 14.4, 1H), 2.15 (s, 3H), 1.68
(s, 3H), 1.22 (t, J = 7.2, 3H), 1.04 (t, J = 7.2, 3H); 13C NMR (75
MHz, CDCl3) δ 171.9, 170.7, 155.7, 142.1, 140.8, 134.1, 129.6,
128.7, 128.2, 126.3, 126.2, 125.9, 125.5, 108.8, 61.4, 61.1, 55.2,
52.5, 43.4, 41.6, 35.0, 32.0, 16.3, 13.9, 13.6; FTIR (film) 2976,
2934, 2834, 1730, 1608, 1504, 1463, 1444, 1366, 1332, 1296, 1245,
1227, 1191, 1167, 1125, 1095, 1051, 1031, 945, 891, 861, 811, 766,
749, 702, 616 cm-1; HRMS (TOF MS ESþ) m/z calcd for
C25H30O5Na [M þ Na]þ 433.1991, found 433.1996.
1H), 1.69 (s, 3H), 1.21 (t, J = 7.2, 3H), 1.00 (t, J = 7.2, 3H); 13
C
NMR (75 MHz, CDCl3) δ 171.9, 170.7, 146.1, 141.8, 140.3,
134.3, 132.7, 128.8, 128.0, 126.6, 126.3, 104.8, 61.5, 61.2, 56.1,
52.5, 43.3, 42.4, 34.9, 32.0, 13.9, 13.6; FTIR (film) 2967, 2934,
1730, 1612, 1519, 1452, 1420, 1366, 1332, 1317, 1243, 1217, 1169,
1113, 1029, 859, 799, 664, 625 cm-1; HRMS (TOF-QII) m/z
calcd for C25H30O7Na [M þ Na]þ 465.1884, found 465.1867.
Compound 14: colorless oil; 90% yield; 1H NMR (300 MHz,
CDCl3) δ 7.20-7.16 (m, 4H), 6.85 (d, J = 6.6, 2H), 6.61 (d,
J = 6.6, 2H), 5.39 (br s, 1H, OH), 4.16 (q, J = 7.2, 1H), 4.15 (q,
J = 7.2, 1H), 3.81 (dq, J = 10.8, 7.2, 1H), 3.45 (dq, J = 10.8, 7.2,
1H), 3.31(d, J= 16.2, 1H), 3.09 (d, J= 16.2, 1H), 2.86 (d, J=14.1,
Compound 9: white crystals; 90% yield; mp 108 °C; 1H NMR
(300 MHz, CDCl3) δ 7.20-7.15 (m, 4H), 6.67 (d, J = 8.4, 1H),
J. Org. Chem. Vol. 75, No. 24, 2010 8445