Journal of Natural Products
Article
withanolides: A (4.0 mg) and B (34.0 mg). Fraction A was fractionated
10.2, 2.5 Hz, H-2), 4.99 (1H, s, H-26), 4.98 (1H, t, J = 7.1 Hz, H-16),
3.66 (1H, brs, H-6), 3.58 (1H, d, J = 11.6 Hz, OH-26), 3.53 (1H, dt, J
= 11.8, 2.8 Hz, H-22), 3.33 (1H, dt, J = 19.6, 2.5 Hz, H-4β), 2.27 (1H,
by preparative TLC with CH Cl −MeOH (94:06) yielding 7 (2.0
2
2
mg), while fraction B was chromatographed with n-hexane−EtOAc
(
30:70) to give 6 (4.0 mg). Fraction IV [EtOAc−MeOH (98:2), 130
ddd, J = 13.6, 6.8, 3.2 Hz, H-11α), 2.07 (3H, s, CH CO-16), 2.06 (1H,
3
mg] was chromatographed on C18 silica gel using MeOH−H O
(
m, H-4α), 1.96 (1H, dt, J = 12.8, 3.3 Hz, H-12β), 1.92 (1H, m, H-20),
1.89 (1H, m, H-23α), 1.81 (1H, m, H-9), 1.75 (1H, m, H-15β), 1.74
(1H, m, H-8), 1.70 (1H, m, H-7β), 1.64 (1H, dd, J = 14.3, 11.5 Hz, H-
23β), 1.51 (1H, t, J = 15.8 Hz, H-14), 1.49 (1H, m, H-7α), 1.48 (1H,
m, H-12α), 1.47 (1H, m, H-15α), 1.41 (6H, s, H -27, H -28), 1.39
2
55:45) as solvent, yielding 5 (41.0 mg). Column chromatography of
fraction V [EtOAc−MeOH (92:8), 65.0 mg] with EtOAc−MeOH
mixtures of increasing polarity gave 8 (7.0 mg).
Salpichrolide O [(17R,20S,22R,24S,25S,26R)-16α-acetoxy-
3
3
5
α,6α:22,26:24,25-triepoxy-26-hydroxyergost-2-en-1-one] (1): col-
(1H, m, H-17), 1.33 (1H, m, H-11β), 1.32 (3H, s, H -19), 0.93 (3H, d,
3
21
13
orless crystals (n-hexane−EtOAc); mp 208 °C (dec); [α] +3.7 (c
J = 6.5 Hz, H -21), 0.77 (3H, s, H -18); C NMR (CDCl , 50.03
D
3
3
3
1
.7, CH Cl ); UV (MeOH) λ (log ε) 220 (3.87) nm; IR (dried
MHz) δ 204.7 (C, C-1), 171.3 (C, CH CO-16), 141.5 (CH, C-3),
2
2
max
3
−1 1
film) νmax 3414, 2930, 1729, 1682, 1378, 1246, 1031 cm ; H NMR
128.6 (CH, C-2), 91.8 (CH, C-26), 79.1 (CH, C-16), 77.4 (C, C-5),
74.1 (CH, C-6), 65.2 (CH, C-22), 64.8 (C, C-24), 63.7 (C, C-25),
58.2 (CH, C-17), 53.1 (CH, C-14), 51.9 (C, C-10), 43.7 (C, C-13),
41.3 (CH, C-9), 40.0 (CH , C-12), 37.6 (CH, C-20), 35.8 (CH , C-4),
(
CDCl −D O (95:05), 400.13 MHz) δ 6.72 (1H, ddd, J = 10.0, 4.9,
3
2
2.2 Hz, H-3), 5.96 (1H, dd, J = 10.0, 2.2 Hz, H-2), 4.97 (1H, sa, J =
11.0 Hz, H-26), 4.96 (1H, t, J = 7.1 Hz, H-16), 3.52 (1H, dt, J = 10.9,
2.9 Hz, H-22), 3.10 (1H, dt, J = 19.6, 2.5 Hz, H-4β), 3.05 (1H, d, J =
4.9 Hz, H-6), 2.31 (1H, ddd, J = 13.6, 7.0, 3.2 Hz, H-11α), 2.07 (3H, s,
2
2
34.3 (CH , C-15), 33.4 (CH , C-23), 29.5 (CH , C-7), 29.4 (CH, C-
2
2
2
8), 22.8 (CH , C-11), 21.2 (CH , CH CO-16), 18.8 (CH , C-28), 16.4
2
3
3
3
CH CO-16), 1.92 (1H, m, H-12β), 1.91 (2H, m, H-7β and, H-23α),
(CH , C-27), 15.6 (CH , C-19), 13.5 (CH , C-18), 12.8 (CH , C-21);
3
3 3 3 3
+
1.87 (1H, m, H-20), 1.84 (1H, dd, J = 19.6, 5.0 Hz, H-4α), 1.74 (1H,
FABMS m/z 555 [M + Na] (17), 429 (5), 381 (12), 341 (94), 313
(69), 155 (33), 136 (72), 123 (41), 111 (32); HRFABMS m/z [M +
m, H-9), 1.69 (1H, m, H-15β), 1.63 (1H, dd, J = 14.1, 11.8 Hz, H-
+
2
3β), 1.44 (1H, m, H-7α), 1.42 (1H, m, H-15α), 1.407 (3H, s, H -27),
Na] 555.2926 (calcd for C H O Na, 555.2934).
3
30 44
8
1
.402 (3H, H -28), 1.40 (1H, m, H-12α), 1.35 (1H, m, H-17), 1.33
Salpichrolide R [(20S,22R,24S,25S,26R)-5α,6α:22,26:24,25-trie-
3
(
1H, m, H-8), 1.33 (3H, s, H-19), 1.31 (1H, m, H-14), 1.30 (1H, m,
poxy-15β,26-dihydroxyergost-2,16-dien-1-one] (4): white, amor-
13
21
H-11β), 0.91 (3H, d, J = 6.8 Hz, H-21), 0.70 (3H, s, H-18); C NMR
phous powder; [α]
D
+9.8 (c 0.13, CH
2
Cl
2
); UV (MeOH) λmax
(
(
(
5
3
1
CDCl , 50.03 MHz) δ 202.7 (C, C-1), 170.9 (C, CH CO-16), 142.2
CH, C-3), 128.9 (CH, C-2), 91.8 (CH, C-26), 78.7 (CH, C-16), 65.0
CH, C-22), 64.7 (C, C-5, C-24), 63.8 (C, C-25), 58.5 (CH, C-6),
(log ε) 222 (3.69) nm; IR (dry film) νmax 3414, 2930, 1729, 1682,
3
3
−1 1
1378, 1246, 1031 cm ; H NMR (CDCl , 400.13 MHz) δ 6.72 (1H,
3
ddd, J = 10.0, 5.0, 2.2 Hz, H-3), 5.96 (1H, dd, J = 10.0, 2.2 Hz, H-2),
5.62 (1H, d, J = 2.6 Hz, H-16), 5.00 (1H, s, H-26), 4.43 (1H, dd, J =
4.8, 2.8 Hz, H-15), 3.77 (1H, ddd, J = 10.5, 7.5, 2.3 Hz, H-22), 3.12
(1H, dt, J = 19.6, 2.8 Hz, H-4β), 3.12 (1H, d, J = 5.1 Hz, H-6), 2.46
(1H, m, H-11α), 2.32 (1H, dt, J = 14.8, 5.5, Hz, H-7β), 2.19 (1H, m,
H-20), 2.00 (1H, dd, J = 14.3, 2.5 Hz, H-23α), 1.85 (1H, dd, J = 19.6,
5.0 Hz, H-4α), 1.81 (1H, m, H-9), 1.75 (1H, m, H-8), 1.63 (1H, m, H-
7.9 (CH, C-17), 54.0 (CH, C-14), 48.3 (C, C-10), 43.2 (C, C-13),
9.5 (CH , C-12), 38.0 (CH, C-9), 37.6 (CH, C-20), 34.4 (CH , C-
2
2
5), 34.0 (CH , C-4), 30.1 (CH, C-8), 29.5 (CH , C-23), 28.6 (CH ,
2
2
2
C-7), 22.3 (CH , C-11), 21.2 (CH , CH CO-16), 18.9 (CH , C-28),
2
3
3
3
1
2
4
1
6.5 (CH , C-27), 15.5 (CH , C-19), 13.2 (CH , C-18), 12.8 (CH , C-
3 3 3 3
+
+
1); FABMS m/z 537 [M + Na] (36), 497 [M + H − H O] (10),
2
68 (9), 342 (22), 341 (84), 313 (37), 193 (35), 155 (41), 123 (64),
23β), 1.62 (1H, m, H-7α), 1.45 (1H, m, H-11β), 1.424 (3H, s, H
1.415 (6H, s, H -27, H -28), 1.23 (1H, dd, J = 10.3, 4.3 Hz, H-14),
1.07 (3H, s, H-18), 0.96 (3H, d, J = 6.9 Hz, H-21); C NMR (CDCl ,
3
3
-19),
11 (52); HRFABMS m/z [M + Na]+ 537.2802 (calcd for
3
3
13
C H O Na, 537.2828).
30
42
7
Salpichrolide P [(17R,20S,22R,24S,25S,26R)-5α,6α:22,26:24,25-
50.03 MHz) δ 202.9 (C, C-1), 162.9 (C, C-17), 142.2 (CH, C-3),
129.0 (CH, C-2), 124.0 (CH, C-16), 91.6 (CH, C-26), 73.6 (CH, C-
15), 66.6 (CH, C-22), 65.0 (C, C-5), 64.6 (C, C-24), 63.7 (C, C-25),
59.6 (CH, C-14), 58.9 (CH, C-6), 48.8 (C, C-10), 47.0 (C, C-13),
39.0 (CH, C-9), 36.4 (CH, C-20), 35.0 (CH , C-23), 34.3 (CH , C-4),
triepoxy-16α,26-dihydroxyergost-2-en-1-one] (2): white, amorphous
powder; [α]21 +35.9 (c 0.4, CH Cl ); UV (MeOH) λ (log ε) 222
D
2
2
max
(
8
1
3.51) nm; IR (dried film) ν 3414, 2925, 1682, 1382, 1087, 1038,
max
−1 1
64, 736 cm ; H NMR (CDCl , 400.13 MHz) δ 6.71 (1H, ddd, J =
3
2
2
0.1, 5.2, 2.2 Hz, H-3), 5.95 (1H, dd, J = 10.1, 1.9 Hz, H-2), 5.02 (1H,
34.2 (CH , C-12), 27.9 (CH , C-7), 26.9 (CH, C-8), 22.8 (CH , C-
2
2
3
brs, H-26), 4.23 (1H, brt, J = 6.7 Hz, H-16), 3.80 (1H, ddd, J = 11.2,
.7, 2.4 Hz, H-22), 3.09 (1H, dt, J = 19.5, 2.5 Hz, H-4β), 3.05 (1H, d, J
4.9 Hz, H-6), 2.28 (1H, ddd, J = 13.6, 7.2, 3.5 Hz, H-11α), 2.08 (1H,
dd, J = 14.3, 2.5 Hz, H-23α), 1.93 (1H, m, H-7β), 1.88 (1H, m, H-
2β), 1.83 (1H, dd, J = 19.5, 5.2 Hz, H-4α), 1.74 (1H, m, H-20), 1.72
1H, m, H-9), 1.60 (1H, m, H-23β), 1.57 (2H, m, H -15), 1.45 (1H,
18), 22.0 (CH , C-11), 18.8 (CH , C-28), 17.4 (CH , C-21), 16.6
2 3 3
+
5
=
(CH , C-27), 15.6 (CH , C-19); EIMS m/z 452 [M − H O] (3), 434
3
3
2
+
[M − 2H O] (4), 422 (8), 404 (30), 389 (20), 328 (8), 310 (24),
309 (27), 171 (24), 123 (100), 109 (28), 91 (18), 55 (22); HREIMS
2
+
1
(
m/z [M − H O] 452.2567 (calcd for C H O , 452.2563).
2
28 36
5
2
Salpichrolide S [(20S,22R,24S,25S,26R)-5α,6α:22,26:24,25-trie-
poxy-1α-O-D-glucosyl-26-hydroxy-17(13→18)abeo-ergosta-
m, H-7α), 1.42 (3H, s, H -27), 1.41 (3H, s, H -28), 1.39 (1H, m, H-
3
3
1
3,15,17-triene] (5): colorless crystals (hexane−EtOAc), mp 153−155
1
1
4), 1.38 (1H, m, H-12α), 1.32 (3H, s, H -19), 1.29 (1H, m, H-8),
3
°
C; [α]21 −53.3 (c 1.2, CH Cl ); UV (MeOH) λ (log ε) 215
−1
.25 (1H, m, H-11β), 1.13 (1H, dd, J = 10.8, 5.6 Hz, H-17), 0.91 (3H,
D
2
2
max
13
(
3.96) nm; IR (dry film) νmax 3416, 2934, 1505, 1081, 1034, 754 cm ;
d, J = 6.8 Hz, H -21), 0.67 (3H, s, H -18); C NMR (CDCl , 50.03
3
3
3
1
H NMR (CDCl −D O (95:05), 400.13 MHz) δ 7.06 (1H, d, J = 8.1
MHz) δ 202.9 (C, C-1), 142.2 (CH, C-3), 129.0 (CH, C-2), 91.8
3
2
(
(
(
(
(
1
2
CH, C-26), 75.1 (CH, C-16), 67.5 (CH, C-22), 65.2 (C, C-5), 64.7
C, C-24), 64.4 (CH, C-17), 63.4 (C, C-25), 58.7 (CH, C-6), 53.4
Hz, H-15), 6.95 (1H, dd, J = 8.1, 1.5 Hz, H-16), 6.89 (1H, brs, H-18),
4.99 (1H, s, H-26), 4.30 (1H, d, J = 7.6 Hz, H-1′), 3.97 (1H, brs, H-1),
3.88 (1H, ddd, J = 10.9, 6.5, 2.1 Hz, H-22), 3.84 (1H, dd, J = 11.9, 3.2
Hz, H-6′a), 3.77 (1H, dd, J = 11.9, 4.7 Hz, H-6′b), 3.52 (1H, t, J = 8.9
Hz, H-4′), 3.49 (1H, t, J = 8.8 Hz, H-3′), 3.42 (1H, t, J = 7.9 Hz, H-
2′), 3.33 (1H, dt, J = 8.1, 4.3 Hz, H-5′), 2.92 (1H, d, J = 4.7 Hz, H-6),
2.81 (1H, m, H-8), 2.80 (1H, m, H-12a), 2.70 (1H, m, H-12b), 2.67
(1H, q, J = 6.8 Hz, H-20), 2.62 (1H, ddd, J = 15.2, 7.8, 4.7 Hz, H-7β),
2.24 (1H, brt, J = 11.9 Hz, H-9), 2.16 (1H, td, J = 13.3, 4.2 Hz, H-2a),
2.06 (1H, brd, J = 14.1 Hz, H-3a), 1.89 (1H, dd, J = 14.2, 2.4 Hz, H-
23α), 1.85 (2H, m, H-2b, H-7α), 1.79 (1H, m, H-11α), 1.57 (1H, dd, J
= 14.2, 11.4 Hz, H-23β), 1.38 (3H, s, H -27), 1.37 (3H, s, H -28), 1.28
CH, C-14), 48.3 (C, C-10), 44.4 (C, C-13), 39.9 (CH , C-12), 38.3
2
CH, C-9), 38.0 (CH, C-20), 36.4 (CH , C-15), 34.0 (CH , C-4), 32.4
2
2
CH , C-23), 30.2 (CH, C-8), 28.7 (CH , C-7), 22.4 (CH , C-11),
2
2
2
8.9 (CH , C-28), 16.4 (CH , C-27), 15.5 (CH , C-19), 14.5 (CH , C-
3
3
3
3
1), 13.5 (CH , C-18); EIMS m/z 424 (10), 406 (10), 472 (3), 312
3
(
4), 283 (25), 163 (21), 123 (100), 109 (43), 97 (17), 55 (24);
+
HRESIMS m/z [M + Na] 495.2729 (calcd for C H O Na,
2
8
40
6
495.2723).
Salpichrolide Q [(17R,20S,22R,24S,25S,26R)-16α-acetoxy-
2
2,26:24,25-diepoxy-5α,6β,26-trihydroxyergost-2-en-1-one] (3):
3
3
21
white, amorphous powder; [α]
+16.7 (c 1.8, CH Cl ); UV
(1H, m, H-11β), 1.21 (3H, d, J = 7.1 Hz, H -21), 1.06 (3H, s, H -19),
3 3
D
2
2
(
MeOH) λmax (log ε) 222 (3.78) nm; IR (dry film) ν
3440,
1.01 (1H, brd, J = 14.1 Hz, H-3b); 13C NMR (CDCl , 100.63 MHz) δ
max
3
−1 1
2935, 1714, 1671, 1380, 1248, 1029 cm ; H NMR (CDCl , 400.13
140.6 (C, C-17), 138.6 (C, C-13), 136.5 (C, C-14), 128.0 (CH, C-18),
3
MHz) δ 6.61 (1H, ddd, J = 10.0, 4.7, 2.0 Hz, H-3), 5.90 (1H, dd, J =
126.4 (CH, C-16), 125.8 (CH, C-15), 105.0 (CH, C-1′), 91.6 (CH, C-
2
223
dx.doi.org/10.1021/np400559p | J. Nat. Prod. 2013, 76, 2219−2225