Paper
Organic & Biomolecular Chemistry
as a mixture of trans and cis isomers (1 : 1), which were inse- 13C-NMR (100 MHz, CDCl3) δ 197.6, 158.9, 137.8, 135.5, 135.2,
parable on a silica gel column. C26H42O5; IR νmax (neat) 2965, 131.3, 124.3, 123.9, 121.2, 69.6, 60.6, 59.5, 44.8, 40.2, 39.8,
2927, 2853, 1673, 1615, 1450, 1265, 1087, 1025, 970, 873, 39.7, 26.7, 26.5, 25.7, 25.5, 17.7, 16.1, 16.0, 11.8. HRMS calcu-
833 cm−1. 1H-NMR (1 : 1 isomers, 400 MHz, CDCl3) δ 5.05 (6 H, lated for C24H38O4: 391.2848, found: m/z 391.2854 [M + H]+.
d, J = 6.0 Hz, olefinic protons), 4.09 (3 H, s, trans), 4.05 (3 H, s,
5-Farnesyl-4-hydroxy-6-methyl-1,2-dimethoxycyclohex-1-en-
cis), 3.63 (6 H, s), 3.28 (3 H, s, cis), 3.27 (3 H, s, trans), 3.24 3-one (13a–13d)
(4,5-cis-5,6-trans)-Isomer 13a. C24H38O4; IR νmax (neat) 3468,
2961, 2920, 1666, 1610, 1456, 1280, 1044, 994, 800, 790 cm−1
(3 H, s, trans), 3.22 (3 H, s, cis), 2.80 (1 H, dt, J = 9.7, 4.4 Hz,
cis), 2.69–2.51 (2 H, m), 2.40 (1 H, qd, J = 7.0, 4.4 Hz, cis),
2.35–2.23 (3 H, m, trans), 2.09–1.88 (17 H, m), 1.63 (6 H, s), 1.60
(6 H, s) 1.55 (12 H, s), 0.94 (3 H, d, J = 6.5 Hz, trans), 0.78 (3 H,
d, J = 7.0 Hz, cis). 13C-NMR (1 : 1 isomers, 100 MHz, CDCl3)
δ 196.4, 196.2, 158.8, 157.3, 145.0, 138.4, 137.2, 136.9, 135.0,
134.9, 131.2, 131.1, 124.4, 124.3, 124.2, 124.1, 124.0, 121.5,
121.4, 101.2, 101.1, 60.8, 60.7, 60.3, 60.2, 51.0, 50.9, 50.7, 49.2,
47.5, 47.0, 42.0, 39.9, 39.8, 39.7 (2×), 37.5, 35.7, 28.9, 26.7, 26.6,
26.5, 25.6 (2×), 24.5, 17.6 (2×), 16.1, 16.0, 15.9, 14.6, 9.4. HRMS
calculated for C26H43O5: 435.3110, found: m/z 435.3104 [M + H]+.
5-Farnesyl-4-hydroxy-6-methyl-2,3-dimethoxycyclohex-2-en-
1-one (1a–1d)
.
1H-NMR (500 MHz, CDCl3) δ 5.10–4.99 (3 H, m), 4.42 (1 H, d,
J = 5.5 Hz), 4.01 (3 H, s), 3.65 (3 H, s), 3.57 (1 H, s), 2.61 (1 H,
qd, J = 7.3, 1.6 Hz), 2.25–2.19 (1 H, m), 2.11–1.90 (9 H, m),
1.79–1.69 (1 H, m), 1.66 (3 H, s), 1.57 (6 H, s), 1.50 (3 H, s),
1.29 (3 H, d, J = 7.3 Hz). 13C-NMR (125 MHz, CDCl3) δ 194.9,
166.7, 138.0, 135.1, 133.5, 131.3, 124.3, 123.9, 121.9, 70.8, 60.6,
59.2, 44.9, 39.8, 39.7, 34.6, 26.7, 26.5, 25.7, 24.0, 17.7, 17.6,
16.1, 16.0. HRMS calculated for C24H38O4: 391.2848, found:
m/z 391.2854 [M + H]+.
(4,5-trans-5,6-trans)-Isomer 13b. C24H38O4; IR νmax (neat)
3470, 2961, 2927, 1666, 1601, 1454, 1301, 1201, 1046, 984, 963,
802 cm−1. 1H-NMR (400 MHz, CDCl3) δ 5.18 (1 H, t, J = 7.5 Hz),
5.05 (2 H, t, J = 6.3 Hz), 4.04 (3 H, s), 3.84 (1 H, d, J = 12.5 Hz),
3.72 (1 H, s), 3.63 (3 H, s), 2.56–2.40 (2 H, m), 2.37–2.25 (1 H,
m), 2.13–1.88 (8 H, m), 1.66 (3 H, s), 1.65 (3 H, s), 1.63–1.60
(1 H, m), 1.59 (3 H, s), 1.57 (3 H, s), 1.19 (3 H, d, J = 7.0 Hz).
13C-NMR (100 MHz, CDCl3) δ 196.2, 167.4, 138.4, 135.1, 133.5,
131.3, 124.3, 124.1, 118.7, 72.2, 60.6, 60.6, 46.1, 40.1, 39.8,
35.3, 26.8, 26.4, 25.7, 25.2, 17.7, 16.3, 16.0, 15.4. HRMS calcu-
lated for C24H38O4: 391.2848, found: m/z 391.2854 [M + H]+.
(4,5-cis-5,6-cis)-Isomer 13c. C24H38O4; IR νmax (neat) 3458,
2966, 2921, 2852, 1665, 1597, 1451, 1309, 1027, 975, 935,
(4,5-cis-5,6-trans)-Isomer 1a (antroquinonol).2,11 C24H38O4;
1H-NMR (500 MHz, CDCl3) δ 5.14 (1 H, t, J = 7.3 Hz), 5.07 (2 H,
t, J = 6.7 Hz), 4.34 (1 H, d, J = 3.1 Hz), 4.05 (3 H, s), 3.65 (3 H,
s), 2.52 (1 H, qd, J = 6.7, 11.0 Hz), 2.22 (2 H, t, J = 7.3 Hz),
2.12–1.92 (8 H, m), 1.74 (1 H, dtd, J = 10.9, 7.5, 3.4 Hz), 1.66
(3 H, s), 1.64 (3 H, s), 1.58 (6 H, s), 1.16 (3 H, d, J = 6.7 Hz).
13C-NMR (125 MHz, CDCl3) δ 197.1, 160.4, 138.1, 135.9, 135.4,
131.1, 124.3, 123.9, 121.0, 68.0, 60.6, 59.2, 43.4, 40.3, 39.8,
39.7, 27.0, 26.8, 26.4, 25.7, 17.7, 16.1, 16.0, 12.3. HRMS calcu-
lated for C24H38O4: 391.2848, found: m/z 391.2854 [M + H]+.
(4,5-trans-5,6-trans)-Isomer 1b. C24H38O4; IR νmax (neat)
3439, 2967, 2851, 1666, 1614, 1450, 1280, 1073, 994, 791,
747 cm−1. 1H-NMR (500 MHz, CDCl3) δ 5.11 (1 H, t, J = 7.3 Hz),
5.05 (2 H, t, J = 6.4 Hz), 4.25 (1 H, d, J = 8.5 Hz), 4.10 (3 H, s),
3.64 (3 H, s), 2.60 (1 H, br s), 2.58–2.51 (1 H, m), 2.24–2.17
(1 H, m), 2.17–1.89 (9 H, m), 1.84–1.77 (1 H, m), 1.65 (6 H, s),
1.57 (6 H, s), 1.19 (3 H, d, J = 6.7 Hz). 13C-NMR (125 MHz,
CDCl3) δ 197.1, 160.3, 138.7, 135.2, 135.2, 131.3, 124.3, 124.0,
118.8, 69.2, 60.7, 60.3, 45.9, 42.0, 40.0, 39.7, 26.7, 26.5, 26.3,
25.7, 17.7, 16.3, 16.0, 13.1. HRMS calculated for C24H39O4:
391.2848, found: m/z 391.2854 [M + H]+.
775 cm−1 1H-NMR (400 MHz, CDCl3) δ 5.14–5.01 (3 H, m),
.
4.12 (1 H, d, J = 2.0 Hz), 4.07 (3 H, s), 3.64 (3 H, s), 3.54 (1 H,
br s), 2.86 (1 H, qd, J = 7.0, 4.5 Hz), 2.25 (1 H, m), 2.10–1.89 (10
H, m), 1.66 (3 H, s), 1.58 (3 H, s), 1.56 (3 H, s), 1.55 (3 H, s),
1.20 (3 H, d, J = 7.0 Hz). 13C-NMR (100 MHz, CDCl3) δ 195.5,
166.8, 135.4, 135.0, 134.3, 131.2, 124.4, 124.1, 123.5, 75.3, 60.7,
60.4, 45.1, 39.8, 39.7, 37.1, 26.7, 26.5, 25.7, 22.1, 17.7, 16.0,
16.0, 15.0. HRMS calculated for C24H38O4: 391.2848, found:
m/z 391.2854 [M + H]+.
(4,5-trans-5,6-cis)-Isomer 13d. C24H38O4; IR νmax (neat) 3450,
2967, 2920, 1666, 1600, 1450, 1280, 1073, 994, 791, 770 cm−1
.
(4,5-cis-5,6-cis)-Isomer 1c. C24H38O4; IR νmax (neat) 3424,
1H-NMR (500 MHz, CDCl3) δ 5.08–5.05 (3 H, m), 4.05 (3 H, s),
3.91 (1 H, d, J = 12.2 Hz), 3.65 (3 H, s), 2.62–2.57 (2 H, m),
2.13–1.88 (10 H, m), 1.66 (3 H, s), 1.64 (3 H, s), 1.58 (6 H, br s),
1.11 (3 H, d, J = 7.3 Hz). 13C-NMR (125 MHz, CDCl3) δ 195.7,
170.2, 137.5, 135.2, 133.6, 131.3, 124.4, 123.9, 120.3, 71.6, 60.8,
59.5, 43.4, 39.8, 39.7, 34.4, 26.8, 26.4 (2×), 25.7, 17.7, 16.3,
16.0, 11.9. HRMS calculated for C24H38O4: 391.2848, found:
m/z 391.2854 [M + H]+.
2922, 2850, 1737, 1612, 1450, 1231, 1043, 1012, 773 cm−1
.
1H-NMR (500 MHz, CDCl3) δ 5.15–5.03 (3 H, m), 4.40 (1 H, br
s), 4.07 (3 H, s), 3.65 (3 H, s), 2.46 (1 H, qd, J = 7.3, 4.3 Hz),
2.38–2.28 (1 H, m), 2.15–1.91 (11 H, m), 1.65 (3 H, s), 1.63
(3 H, s), 1.57 (6 H, s), 1.23 (3 H, d, J = 7.3 Hz). 13C-NMR
(125 MHz, CDCl3) δ 199.2, 160.6, 137.4, 135.3, 135.2, 131.3,
124.3, 123.9, 121.5, 69.7, 60.5, 59.6, 44.1, 40.3, 39.8, 39.7, 26.8,
26.5, 25.7, 25.6, 17.7, 16.2, 16.0, 14.8. HRMS calculated for
C24H38O4: 391.2848, found: m/z 391.2854 [M + H]+.
(4,5-trans-5,6-cis)-Isomer 1d. C24H38O4; IR νmax (neat) 3431,
2976, 2919, 2849, 1667, 1614, 1451, 1234, 1039, 969, 781,
Acknowledgements
750 cm−1 1H-NMR (400 MHz, CDCl3) δ 5.13–5.02 (3 H, m),
.
We thank the Ministry of Science and Technology in Taiwan
for financial support and the Golden Biotechnology Corpor-
ation in Taiwan for providing the authentic sample of natural
(+)-antroquinonol for spectral comparison.
4.29 (1 H, d, J = 4.4 Hz), 4.05 (3 H, s), 3.65 (3 H, s), 2.88 (1 H,
qd, J = 6.8, 3.8 Hz), 2.38 (1 H, br s), 2.13–1.90 (11 H, m), 1.65
(3 H, s), 1.57 (6 H, s), 1.54 (3 H, s), 1.08 (3 H, d, J = 6.8 Hz).
5518 | Org. Biomol. Chem., 2015, 13, 5510–5519
This journal is © The Royal Society of Chemistry 2015