5856
W.-J. Zhang et al. / Tetrahedron 69 (2013) 5850e5858
J¼7.2 Hz, 1H, 3-CH2CH]), 3.98 (s, 3H, OCH3), 3.14 (br d, J¼6.8 Hz,
2H, 3-CH2CH]), 2.43e2.48 (m, 1H, eCHMe2), 1.58, 1.45 (each br s,
6H, 2ꢂ CH3), 1.10 (d, J¼6.8 Hz, 6H, 2ꢂ CH3). 13C NMR (100 MHz,
OCH3), 3.06 (d, J¼6.4 Hz, 2H, eCOCH2e), 3.03 (br d, J¼6.8 Hz, 2H,
3-CH2CH]), 2.26e2.33 (m, 1H, eCHMe2), 1.62, 1.42 (each br s, 6H,
2ꢂ CH3), 1.00 (d, J¼6.4 Hz, 6H, 2ꢂ CH3). 13C NMR (100 MHz, CDCl3):
acetone-d6):
d
182.4, 163.0, 161.6, 160.6, 159.0, 156.5, 156.3, 141.3,
d 206.9, 182.7, 169.2, 167.4, 161.9, 160.9, 160.6, 159.5, 158.2, 132.4,
131.4, 131.3, 121.6, 121.1, 116.1, 112.0, 108.9, 107.2, 104.7, 103.0, 89.6,
55.7, 33.1, 24.9, 23.8, 22.2, 16.8. ESI-MS: [MꢁH]ꢁ 435.2; HRMS (ESI)
calcd for C26H27O6 [MꢁH]ꢁ 435.1813, found 435.1803.
131.2, 129.2, 128.1, 121.1, 120.8, 114.0, 106.1, 105.2, 103.3, 99.5, 94.5,
70.0, 55.5, 55.2, 53.1, 25.6, 24.9, 24.0, 22.6, 17.5. ESI-MS: [MþH]þ
573.1; HRMS (ESI) calcd mass for C34H37O8 [MþH]þ 573.2483,
found 573.2471.
4.15. 5,7-Dihydroxy-2-(2-hydroxy-4-methoxyphenyl)-3-(3-
methylbut-2-en-1-yl)-6-(3-methylbutanoyl)-4H-chromen-4-
one (20a) and 5,7-dihydroxy-2-(4-hydroxy-2-methoxyphenyl)-
3-(3-methylbut-2-en-1-yl)-6-(3-methylbutanoyl)-4H-chro-
men-4-one (20b)
4.17. 5,7-Dihydroxy-2-(4-hydroxy-2-((4-methoxybenzyl)oxy)
phenyl)-3-(3-methylbut-2-en-1-yl)-6-(3-methylbutanoyl)-4H-
chromen-4-one (22)
According to the previous procedure, compounds 22 and 20a
were obtained in 61% and 22% yields, respectively. 22: a light yellow
Compounds 20a and 20b were prepared according to the pre-
vious procedure in 88% yield with a 1:1 ratio. 20a: a yellow oil. IR
(neat):
oil. IR (neat):
n
3368, 2925, 1632, 1582, 1454, 1379, 1172, 1012,
15.62, 14.24 (each s, 2H, 2ꢂ
n ;
3401, 2959, 1624, 1584, 1456, 1377, 1172, 1035, 823 cmꢁ1
822 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d
1H NMR (400 MHz, acetone-d6):
d
15.97, 14.15, 9.03 (each s, 3H, 3ꢂ
AreOH), 7.24 (d, J¼8.4 Hz, 2H, AreH), 7.18 (d, J¼8.0 Hz, 1H, AreH),
6.84 (d, J¼8.4 Hz, 2H, AreH), 6.57 (d, J¼2.4 Hz, 1H, AreH), 6.49 (dd,
J¼8.0, 2.4 Hz, 1H, AreH), 6.25 (s, 1H, AreH), 5.07 (br t, J¼6.8 Hz, 1H,
3-CH2CHe), 5.00 (s, 2H, ArCH2Oe), 3.78 (s, 3H, OCH3), 3.05 (d,
J¼6.8 Hz, 4H, 2ꢂ CH2), 2.28e2.31 (m, 1H, eCHMe2), 1.56, 1.44 (each
br s, 6H, 2ꢂ CH3), 1.00 (d, J¼6.8 Hz, 6H, 2ꢂ CH3). 13C NMR (100 MHz,
AreOH), 7.33 (d, J¼9.0 Hz, 1H, AreH), 6.62e6.64 (m, 2H, AreH),
6.27 (s, 1H, AreH), 5.11 (br t, J¼7.0 Hz, 1H, 3-CH2CH]), 3.84 (s, 3H,
OCH3), 3.12 (br d, J¼7.0 Hz, 2H, 3-CH2CH]), 3.08 (d, J¼6.7 Hz, 2H, 6-
COCH2e), 2.24e2.31 (m, 1H, eCHMe2), 1.58, 1.44 (each br s, 6H, 2ꢂ
CH3), 1.01 (d, J¼6.4 Hz, 6H, 2ꢂ CH3). 13C NMR (100 MHz, acetone-
d6): d 206.6, 182.8, 169.3, 167.5, 163.0, 161.9, 160.7, 156.3, 131.9, 131.4,
CDCl3):
d 207.2, 182.9, 169.3, 167.6, 161.5, 160.7, 159.4, 159.3, 157.9,
121.1, 121.0, 112.4, 106.0, 105.7, 103.1, 101.7, 94.2, 54.9, 52.8, 24.9,
24.6, 23.7, 22.1, 16.8. ESI-MS: [MꢁH]ꢁ 451.1; HRMS (ESI) calcd for
C26H29O7 [MþH]þ 453.1907, found 453.1895. 20b: a yellow oil. IR
132.7, 131.6, 128.8, 128.1, 121.2, 121.0, 114.2, 114.0, 107.6, 106.3, 103.5,
101.0, 94.6, 70.3, 55.3, 53.2, 25.7, 25.0, 24.3, 22.8, 17.6. ESI-MS:
[MꢁH]ꢁ 557.2; HRMS (ESI) calcd for C33H34O8Na [MþNa]þ
581.2146, found 581.2135.
(neat):
n 3408, 2959, 1636, 1584, 1457, 1382, 1307, 1177, 960, 887,
822 cmꢁ1; 1H NMR (400 MHz, acetone-d6):
d 15.96,14.15, 9.08 (each
s, 3H, 3ꢂ AreOH), 7.28 (d, J¼8.0 Hz,1H, AreH), 6.65 (d, J¼2.0 Hz,1H,
AreH), 6.60 (dd, J¼8.0, 2.0 Hz, 1H, AreH), 6.24 (s, 1H, AreH), 5.09
(br t, J¼7.2 Hz, 1H, 3-CH2CH]), 3.82 (s, 3H, OCH3), 3.08 (d, J¼6.8 Hz,
2H, 6-COCH2e), 3.04 (br d, J¼7.2 Hz, 2H, 3-CH2CH]), 2.28e2.33 (m,
1H, eCHMe2), 1.59, 1.42 (each br s, 6H, 2ꢂ CH3), 1.01 (d, J¼6.8 Hz,
4.18. 2-(2,4-Dihydroxyphenyl)-5,7-dihydroxy-3-(3-methylbut-
2-en-1-yl)-6-(3-methylbutanoyl)-4H-chromen-4-one (23)
Compound 23 was prepared as a yellow powder in 38% yield
according to the previous procedure, mp 183e185 ꢀC. IR (neat):
n
6H, 2ꢂ CH3). 13C NMR (100 MHz, acetone-d6):
d 207.5, 183.6, 170.2,
3292, 1623, 1581, 1452, 1367, 1173, 820 cmꢁ1
;
1H NMR (400 MHz,
16.02, 14.14 (each s, 2H, 2ꢂ AreOH), 8.91, 8.86 (each
168.4,163.0, 162.1,161.6, 159.7, 132.6, 132.3, 122.0, 121.7, 113.5, 108.2,
107.0, 103.9, 100.2, 95.1, 56.1, 53.7, 25.8, 25.5, 24.6, 23.0, 17.6; ESI-
MS: [MꢁH]ꢁ 451.1; HRMS (ESI) calcd mass for C26H27O7 [MꢁH]ꢁ
451.1762, found 451.1773.
acetone-d6):
d
br s, 2H, 2ꢂ AreOH), 7.23 (d, J¼8.4 Hz, 1H, AreH), 6.57 (d, J¼2.0 Hz,
1H, AreH), 6.53 (dd, J¼8.4, 2.0 Hz, 1H, AreH), 6.28 (s, 1H, AreH),
5.12 (br t, J¼6.8 Hz, 1H, 3-CH2CH]), 3.13 (br d, J¼6.8 Hz, 2H, 3-
CH2CH]), 3.08 (d, J¼6.4 Hz, 2H, 6-COCH2e), 2.26e2.33 (m, 1H,
eCHMe2), 1.58, 1.44 (each br s, 6H, 2ꢂ CH3), 1.00 (d, J¼6.4 Hz, 6H,
4.16. 5,7-Dihydroxy-2-(4-methoxy-2-((4-methoxybenzyl)oxy)
phenyl)-3-(3-methylbut-2-en-1-yl)-6-(3-methylbutanoyl)-4H-
chromen-4-one (21a) and 5,7-dihydroxy-2-(2-methoxy-4-((4-
methoxybenzyl)oxy)phenyl)-3-(3-methylbut-2-en-1-yl)-6-(3-
methylbutanoyl)-4H-chromen-4-one (21b)
2ꢂ CH3). 13C NMR (100 MHz, acetone-d6):
d 207.4, 183.7, 170.2,
168.4, 163.1, 161.7, 161.6, 157.3, 132.7, 132.3, 130.4, 122.0, 121.6, 114.2,
112.1, 108.2, 103.8, 95.0, 53.6, 25.8, 25.4, 24.6, 23.0, 17.6. ESI-MS
[MꢁH]ꢁ: 437.1; HRMS (ESI) calcd mass for C25H25O7 [MꢁH]ꢁ
437.1606, found 437.1623.
Compounds 21a and 21b were prepared according to the pre-
vious procedure. 21a: a yellow oil, 97% yield. IR (neat):
1632, 1582, 1457, 1380, 1172, 1037, 823 cmꢁ1 1H NMR (400 MHz,
CDCl3):
n 3462, 2958,
;
4.19. 2-(2,4-Dihydroxyphenyl)-5,7-dihydroxy-6-(1-hydroxy-3-
methylbutyl)-3-(3-methylbut-2-en-1-yl)-4H-chromen-4-one
(24)
d
15.64, 14.23 (each s, 2H, 2ꢂ AreOH), 7.21e7.24 (m, 3H,
AreH), 6.84 (d, J¼8.8 Hz, 2H, AreH), 6.61 (d, J¼2.0 Hz, 1H, AreH),
6.57 (dd, J¼8.4, 2.0 Hz, 1H, AreH), 6.24 (s, 1H, AreH), 5.05 (br t,
J¼6.8 Hz, 1H, 3-CH2CH]), 5.01 (s, 2H, ArCH2Oe), 3.84, 3.77 (each s,
6H, 2ꢂ OCH3), 3.05 (d, J¼6.8 Hz, 4H, 2ꢂ CH2), 2.26e2.32 (m, 1H,
eCHMe2), 1.61, 1.43 (each br s, 6H, 2ꢂ CH3),1.00 (d, J¼6.8 Hz, 6H, 2ꢂ
Compound 24 was prepared as a yellow oil in 99% yield
according to the previous procedure. IR (neat):
1433, 1363, 1228, 1152, 978, 845, 811 cmꢁ1 1H NMR (400 MHz,
acetone-d6): 13.59 (s, 1H, AreOH), 10.26 (br s, 1H, AreOH), 8.81
n 3236, 1705, 1621,
;
CH3). 13C NMR (100 MHz, CDCl3):
d
207.0, 182.9, 169.4, 167.6, 162.8,
d
161.3, 160.7, 159.4, 157.6, 132.6, 131.5, 128.8, 128.2, 121.1, 114.6, 114.0,
106.3, 105.1, 103.4, 100.4, 94.5, 70.4, 55.6, 55.2, 53.2, 25.7, 25.0, 24.3,
22.8, 17.7. ESI-MS: [MꢁH]ꢁ 571.2; HRMS (ESI) calcd for C34H37O8
[MþH]þ 573.2483, found 573.2470. 21b: a yellow oil, 66% yield. IR
(br s, 2H, 2ꢂ AreOH), 6.93 (d, J¼7.2 Hz,1H, AreH), 6.52 (d, J¼2.0 Hz,
1H, AreH), 6.48 (dd, J¼7.2, 2.0 Hz, 1H, AreH), 6.32 (s, 1H, AreH),
5.39e5.41 (m,1H, 6-CH(OH)e), 5.07 (br t, J¼6.8 Hz,1H, 3-CH2CH]),
3.05 (br d, 2H, 3-CH2CH]), 1.73e1.89 (m, 2H, eCH2CHMe2),
1.48e1.50 (m, 1H, eCHMe2), 1.52, 1.38 (each br s, 6H, 2ꢂ CH3), 0.93
(neat):
n 3435, 3388, 1636, 1582, 1446, 1383, 1280, 1174, 1040,
820 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d
15.65, 14.21 (each s, 2H, 2ꢂ
(d, J¼6.4 Hz, 6H, 2ꢂ CH3). 13C NMR (100 MHz, acetone-d6):
d 183.2,
AreOH), 7.37 (d, J¼8.4 Hz, 2H, AreH), 7.23 (d, J¼8.4 Hz, 1H, AreH),
6.94 (d, J¼8.4 Hz, 2H, AreH), 6.64 (dd, J¼8.4, 2.4 Hz, 1H, AreH), 6.61
(d, J¼2.4 Hz, 1H, AreH), 6.25 (s, 1H, AreH), 5.07e5.09 (m, 1H, 3-
CH2CH]), 5.07 (s, 2H, ArCH2Oe), 3.83, 3.78 (each s, 6H, 2ꢂ
164.2, 162.4, 161.4, 158.4, 157.8, 157.2, 132.1, 130.4, 122.5, 121.4, 114.1,
112.8, 112.3, 107.9, 103.7, 94.9, 67.6, 46.5, 25.7, 25.2, 24.5, 23.7, 22.0,
17.5. ESI-MS: [MꢁH]ꢁ 439.2; HRMS (ESI) calcd mass for C25H27O7
[MꢁH]ꢁ 439.1762, found 439.1760.