Journal of Natural Products
Article
CH2, C-2′, C4′−C-7′), 25.8 (CH2, C-3′); HRESIMS m/z 539.2759
(calcd for C33H40O5Na, 539.2773).
Compound 23. According to the general procedure, 14 (0.5 mmol,
200 mg) was reduced with H2 to give 23 (100 mg, 88%): syrup; IR
(film) νmax 3390, 1715, 1228 cm−1; 1H NMR (CDCl3, 400.45 MHz) δ
6.79 (1H, d, J = 8.0 Hz, H-6), 6.74 (1H, brs, H-3), 6.65 (1H, d, J = 8.0
Hz, H-5), 4.28 (2H, t, J = 7.0 Hz, H-8), 4.19 (2H, q, J = 7.2 Hz, H-1′),
2.86 (2H, t, J = 7.0 Hz, H-7), 1.30 (3H, t, J = 7.2 Hz, H-2′); 13C NMR
(CDCl3, 100.70 MHz) δ 155.4 (C, CO), 143.7 (C, C-2), 142.5 (C,
C-1), 130.3 (C, C-4), 121.6 (CH, C-5), 116.1 (CH, C-3), 115.6 (CH,
C-6), 68.6 (CH2, C-8), 64.3 (CH2, C-1′), 34.6 (CH2, C-7), 14.4 (CH3,
C-2′); HRESIMS m/z 249.0737 (calcd for C11H14O5Na, 249.0739).
Compound 24. According to the general procedure, 15 (0.46
mmol, 200 mg) was reduced with H2 to give 24 (105 mg, 89%): syrup;
IR (film) νmax 3408, 1715, 1275 cm−1; 1H NMR (CDCl3, 400.45
MHz) δ 6.79 (1H, d, J = 8.0 Hz, H-6), 6.73 (1H, brs, H-3), 6.64 (1H,
d, J = 8.0 Hz, H-5), 4.28 (2H, t, J = 7.0 Hz, H-8), 4.19 (2H, t, J = 7.2
Hz, H-1′), 2.86 (2H, t, J = 7.0 Hz, H-7), 1.64 (2H, quint, J = 7.2 Hz,
H-2′), 1.39 (2H, sext, J = 7.2 Hz, H-3′), 0.93 (3H, t, J = 7.2 Hz, H-4′);
13C NMR (CDCl3, 100.70 MHz) δ 155.6 (C, CO), 143.7 (C, C-2),
142.5 (C, C-1), 130.3 (C, C-4), 121.5 (CH, C-5), 116.1 (CH, C-3),
115.6 (CH, C-6), 68.6 (CH2, C-8), 68.2 (CH2, C-1′), 34.6 (CH2, C-
7), 30.8 (CH2, C-2′), 19.0 (CH2, C-3′), 13.8 (CH3, C-4′); HRESIMS
m/z 277.1049 (calcd for C13H18O5Na, 277.1052).
Compound 25. According to the general procedure, 16 (0.43
mmol, 200 mg) was reduced with H2 to give 25 (111 mg, 91%): syrup;
IR (film) νmax 3402, 1715, 1249 cm−1; 1H NMR (CDCl3, 499.79
MHz) δ 6.79 (1H, d, J = 8.5 Hz, H-6), 6.75 (1H, brs, H-3), 6.65 (1H,
d, J = 8.5 Hz, H-5), 4.28 (2H, t, J = 7.2 Hz, H-8), 4.11 (2H, t, J = 6.5
Hz, H-1′), 2.86 (2H, t, J = 7.2 Hz, H-7), 1.68−1.62 (2H, m, H-2′),
1.38−1.26 (6H, m, H-3′, H-4′, and H-5′), 0.89 (3H, t, J = 6.5 Hz, H-
6′); 13C NMR (CDCl3, 125.68 MHz) δ 155.5 (C, CO), 143.7 (C,
C-2), 142.4 (C, C-1), 130.4 (C, C-4), 121.6 (CH, C-5), 116.2 (CH, C-
3), 115.6 (CH, C-6), 68.5 (CH2, C-8), 68.4 (CH2, C-1′), 34.6 (CH2,
C-7), 31.5 (CH2, C-4′), 28.8 (CH2, C-2′), 25.5 (CH2, C-3′), 22.7
(CH2, C-5′), 14.1 (CH3, C-6′); HRESIMS m/z 305.1364 (calcd for
C15H22O5Na, 305.1365).
Compound 19. According to the general procedure, 13 (396 mg)
reacted with dodecan-1-ol (240 mg) to give 19 (445 mg, 81%): syrup;
IR (film) νmax 2920, 1743, 1253 cm−1; 1H NMR (CDCl3, 400.45
MHz) δ 7.46−7.29 (10H, m, aromatic H), 6.87 (1H, d, J = 8.0 Hz, H-
6), 6.83 (1H, brs, H-3), 6.74 (1H, d, J = 8.0 Hz, H-5), 5.14 and 5.13
(each 2H, collapsed AB systems, Ph-CH2-O), 4.26 (2H, t, J = 7.2 Hz,
H-8), 4.12 (2H, t, J = 6.8 Hz, H-1′), 2.88 (2H, t, J = 7.2 Hz, H-7), 1.65
(2H, m, H-2′), 1.26 (18H, m, H-3′−H-11′), 0.88 (3H, t, J = 6.8 Hz,
H-12′); 13C NMR (CDCl3, 100.70 MHz) δ 155.4 (C, CO), 149.2
(C, C-2), 148.0 (C, C-1), 137.6 and 137.4 (2 aromatic C), 130.8 (C,
C-4), 128.6, 127.9, 127.8, 127.5, and 127.4 (10 aromatic CH), 122.0
(CH, C-5), 116.2 (CH, C-3), 115.5 (CH, C-6), 71.6 and 71.5 (2 Ph-
CH2-O), 68.4 (CH2, C-8), 68.3 (CH2, C-1′), 34.8 (CH2, C-7), 32.1
(CH2, C-10′), 29.8, 29.7, 29.7, 29.6, 29.5, 29.4, and 28.8 (each CH2, C-
2′, C-4′−C-9′), 25.8 (CH2, C-3′), 22.8 (CH2, C-11′), 14.3 (CH3, C-
12′); HRESIMS m/z 569.3247 (calcd for C35H46O5Na, 569.3243).
Compound 20. According to the general procedure, 13 (396 mg)
reacted with tetradecan-1-ol (278 mg) to give 20 (438 mg, 76%):
syrup; IR (film) νmax 2922, 2825, 1742, 1253 cm−1; 1H NMR (CDCl3,
400.45 MHz) δ 7.46−7.29 (10H, m, aromatic H), 6.87 (1H, d, J = 8.2
Hz, H-6), 6.83 (1H, brs, H-3), 6.74 (1H, d, J = 8.2 Hz, H-5), 5.14 and
5.13 (each 2H, collapsed AB systems, Ph-CH2-O), 4.26 (2H, t, J = 7.6
Hz, H-8), 4.11 (2H, t, J = 6.8 Hz, H-1′), 2.89 (2H, t, J = 7.6 Hz, H-7),
1.65 (2H, m, H-2′), 1.26 (22H, m, H-3′−H-13′), 0.88 (3H, t, J = 6.8
Hz, H-14′); 13C NMR (CDCl3, 100.70 MHz) δ 155.4 (C, CO),
149.2 (C, C-2), 148.0 (C, C-1), 137.6 and 137.4 (2 aromatic C), 130.8
(C, C-4), 128.6, 127.9, 127.8, 127.5, and 127.4 (10 aromatic CH),
122.0 (CH, C-5), 116.2 (CH, C-3), 115.5 (CH, C-6), 71.6 and 71.5 (2
Ph-CH2-O), 68.4 (CH2, C-8), 68.3 (CH2, C-1′), 34.8 (CH2, C-7), 32.1
(CH2, C-12′), 29.8, 29.7, 29.7, 29.6, 29.6, 29.5, 29.5, 29.4, and 28.8
(each CH2, C-2′, C-4′−C-11′), 25.8 (CH2, C-3′), 22.8 (CH2, C-13′),
14.3 (CH3, C-14′); HRESIMS m/z 597.3535 (calcd for C37H50O5Na,
597.3556).
Compound 26. According to the general procedure, 17 (0.41
mmol, 200 mg) was reduced with H2 to give 26 (114 mg, 89%): syrup;
IR (film) νmax 3392, 2925, 1720, 1250 cm−1; 1H NMR (CDCl3, 499.79
MHz) δ 6.79 (1H, d, J = 8.0 Hz, H-6), 6.75 (1H, brs, H-3), 6.65 (1H,
d, J = 8.0 Hz, H-5), 4.27 (2H, t, J = 7.0 Hz, H-8), 4.11 (2H, t, J = 6.5
Hz, H-1′), 2.86 (2H, t, J = 7.0 Hz, H-7), 1.65 (2H, m, H-2′), 1.35−
1.25 (10H, m, H-3′−H-7′), 0.88 (3H, t, J = 6.5 Hz, H-8′); 13C NMR
(CDCl3, 125.68 MHz) δ 155.5 (C, CO), 143.7 (C, C-2), 142.4 (C,
C-1), 130.5 (C, C-4), 121.6 (CH, C-5), 116.1 (CH, C-3), 115.6 (CH,
C-6), 68.5 (CH2, C-8), 68.4 (CH2, C-1′), 34.6 (CH2, C-7), 31.9 (CH2,
C-6′), 29.3, 29.2, and 28.8 (each CH2, C-2′, C-4′, and C-5′), 25.8
(CH2, C-3′), 22.8 (CH2, C-7′), 14.1 (CH3, C-8′); HRESIMS m/z
333.1674 (calcd for C17H26O5Na, 333.1678).
Compound 27. According to the general procedure, 18 (0.39
mmol, 200 mg) was reduced with H2 to give 27 (117 mg, 89%): syrup;
IR (film) νmax 3410, 2923, 1718, 1249 cm−1; 1H NMR (CDCl3, 499.79
MHz) δ 6.79 (1H, d, J = 8.0 Hz, H-6), 6.74 (1H, brs, H-3), 6.65 (1H,
d, J = 8.0 Hz, H-5), 4.27 (2H, t, J = 7.5 Hz, H-8), 4.11 (2H, t, J = 6.5
Hz, H-1′), 2.86 (2H, t, J = 7.5 Hz, H-7), 1.65 (2H, quint, J = 6.5 Hz,
H-2′), 1.40−1.22 (14H, m, H-3′−H-9′), 0.88 (3H, t, J = 6.5 Hz, H-
10′); 13C NMR (CDCl3, 125.68 MHz) δ 155.5 (C, CO), 143.7 (C,
C-2), 142.4 (C, C-1), 130.4 (C, C-4), 121.6 (CH, C-5), 116.1 (CH, C-
3), 115.6 (CH, C-6), 68.5 (CH2, C-8), 68.4 (CH2, C-1′), 34.6 (CH2,
C-7), 32.0 (CH2, C-8′), 29.7, 29.6, 29.4, 29.3, and 28.8 (each CH2, C-
2′, C-4′−C-7′), 25.8 (CH2, C-3′), 22.8 (CH2, C-9′), 14.3 (CH3, C-
10′); HRESIMS m/z 361.1991 (calcd for C19H30O5Na, 361.1991).
Compound 28. According to the general procedure, 19 (0.37
mmol, 200 mg) was reduced with H2 to give 28 (121 mg, 89%): syrup;
IR (film) νmax 3405, 2923, 1718, 1280 cm−1; 1H NMR (CDCl3, 600.24
MHz) δ 6.79 (1H, d, J = 8.0 Hz, H-6), 6.75 (1H, brs, H-3), 6.66 (1H,
d, J = 8.0 Hz, H-5), 4.27 (2H, t, J = 6.0 Hz, H-8), 4.11 (2H, t, J = 6.5
Hz, H-1′), 2.86 (2H, t, J = 6.0 Hz, H-7), 1.65 (2H, quint, J = 6.5 Hz,
H-2′), 1.36−1.26 (18H, m, H-3′−H-11′), 0.88 (3H, t, J = 6.5 Hz, H-
12′); 13C NMR (CDCl3, 150.95 MHz) δ 155.5 (C, CO), 143.7 (C,
C-2), 142.4 (C, C-1), 130.5 (C, C-4), 121.6 (CH, C-5), 116.1 (CH, C-
Compound 21. According to the general procedure, 13 (396 mg)
reacted with hexadecan-1-ol (314 mg) to give 21 (498 mg, 82%):
syrup; IR (film) νmax 2917, 2850, 1740, 1251 cm−1; 1H NMR (CDCl3,
400.45 MHz) δ 7.46−7.30 (10H, m, aromatic H), 6.89 (1H, d, J = 8.0
Hz, H-6), 6.84 (1H, brs, H-3), 6.74 (1H, d, J = 8.0 Hz, H-5), 5.14 and
5.13 (each 2H, collapsed AB systems, Ph-CH2-O), 4.26 (2H, t, J = 7.4
Hz, H-8), 4.11 (2H, t, J = 6.8 Hz, H-1′), 2.88 (2H, t, J = 7.4 Hz, H-7),
1.66 (2H, m, H-2′), 1.26 (26H, m, H-3′−H-15′), 0.88 (3H, t, J = 6.8
Hz, H-16′); 13C NMR (CDCl3, 100.70 MHz) δ 155.6 (C, CO),
149.2 (C, C-2), 148.0 (C, C-1), 137.5 and 137.4 (2 aromatic C), 130.8
(C, C-4), 128.6, 127.9, 127.8, 127.5, and 127.4 (10 aromatic CH),
122.0 (CH, C-5), 116.2 (CH, C-3), 115.5 (CH, C-6), 71.6 and 71.5 (2
Ph-CH2-O), 68.4 (CH2, C-8), 68.3 (CH2, C-1′), 34.8 (CH2, C-7), 32.1
(CH2, C-14′), 31.1 (CH2, C-2′), 29.9, 29.9, 29.8, 29.8, 29.7, 29.7, 29.6,
29.5, 29.4, and 28.8 (each CH2, C-4′−C-13′), 25.8 (CH2, C-3′), 22.8
(CH2, C-15′), 14.3 (CH3, C-16′); HRESIMS m/z 625.3872 (calcd for
C39H54O5Na, 625.3869).
Compound 22. According to the general procedure, 13 (396 mg)
reacted with 8 (468 mg) to give 22 (520 mg, 83%): syrup; IR (film)
νmax 1599, 1510, 1253, 1222 cm−1; 1H NMR (CDCl3, 400.45 MHz) δ
7.46−7.30 (20H, m, aromatic H), 6.87 (2H, d, J = 8.0 Hz, H-6), 6.83
(2H, brs, H-3), 6.74 (2H, d, J = 8.0 Hz, H-5), 5.14 and 5.13 (each 2H,
4 collapsed AB systems, Ph-CH2-O), 4.26 (4H, t, J = 6.0 Hz, H-8),
2.87 (4H, t, J = 6.0 Hz, H-7); 13C NMR (CDCl3, 100.70 MHz) δ
155.2 (C, CO), 149.1 (C, C-2), 148.0 (C, C-1), 137.5 and 137.4 (4
aromatic C), 130.7 (C, C-4), 128.4, 127.9, 127.8, 127.6, and 127.4 (20
aromatic CH), 122.0 (CH, C-5), 116.2 (CH, C-3), 115.1 (CH, C-6),
71.6 and 71.5 (4 Ph-CH2-O), 68.5 (CH2, C-8), 34.8 (CH2, C-7);
HRESIMS m/z 717.2839 (calcd for C45H42O7Na, 717.2828).
General Method for Debenzylation. A solution of the correspond-
ing dibenzylated compound (14−22), in EtOH, was reduced with
Pd−C under a H2 atmosphere, under the same conditions described
above for compounds 7 and 8, yielding respectively compounds 23−
31.
G
J. Nat. Prod. XXXX, XXX, XXX−XXX