Y. Chen et al.
Bioorganic Chemistry 107 (2021) 104530
2
D
5
Table 1
Eremofortin G (2): colorless oil; [
α
]
+18 (c 0.20, MeOH); UV
): 235(3.50) nm; IR (KBr) max: 3453, 2947, 1735,
626, 1433, 1342, 1228 cm ; H and C NMR data, see Tables 1 and 2;
1
H NMR (500 MHz) spectroscopic data for compounds 2 and 4–6 in CDCl (δ in
ppm, J in Hz).
3
(
MeOH) λmax (log
ε
ν
ꢀ 1
1
13
1
+
no.
1
2
4
5
6
HRESIMS m/z 431.27928 [M + H] (calcd for C26
H
39
O
, 431.27920).
+23 (c 0.22, MeOH); UV
): 234(3.47) nm; IR (KBr) max: 3426, 2952, 1726,
5
2
5
2.49, dt (4.5,
2.49, dt (3.4,
14.6)
2.49, m
2.32, m
Eremofortin H (4): colorless oil; [α]
D
1
2
5.0)
(
MeOH) λmax (log
ε
ν
13
.35, m
2.35, m
2.36, m
2.16, m
ꢀ 1
1
1
656, 1450, 1368, 1260, 1172 cm ; H and C NMR data, see Tables 1
2
2.17, m
2.17, q (12.3)
2.18, q (11.5)
2.03, dt (3.4,
.3)
1.40, dd (4.4,
4.3)
+
and 2; HRESIMS m/z 447.27375 [M + H] (calcd for C26
39 6
H O ,
8
1
.48, m
1.49, brd (13.9)
1.48, brd (10.2)
447.27412).
1
25
D
Eremofortin I (5): colorless oil; [
α
]
+18 (c 0.20, MeOH); UV
max: 3436, 2942, 1718,
635, 1443, 1352, 1236 cm ; H and C NMR data, see Tables 1 and 2;
3
4
6
4.89, dt (4.4,
1.6)
4.91, dt (4.4,
11.1)
4.91, dt (4.4,
11.1)
4.85, m
1.54, m
1.60, m
(
MeOH) λmax (log
ε
): 235(3.50) nm; IR (KBr)
ν
1
ꢀ 1
1
13
1
1.65, m
1.63, m
1.63, qd (6.7,
+
1
1.0)
HRESIMS m/z 447.27364 [M + H] (calcd for C26
39 6
H O , 447.27412).
2.04, dd (4.5,
2.03, dd (4.5,
13.0)
2.03, dd (4.5,
13.0)
25
D
Eremofortin J (6): colorless oil; [
α
]
+16 (c 0.25, MeOH); UV
max: 3432, 2967, 1716,
1
1
3.1)
(
MeOH) λmax (log
ε
): 235(3.56) nm; IR (KBr)
ν
.89, t (13.1)
1.90, m
1.87, m
ꢀ
1
1
13
7
3.13, dd (4.5,
4.4)
3.11, dd (4.5,
14.4)
3.11, dd (4.5,
14.4)
2.24, m
1662, 1462, 1375, 1258, 1176 cm ; H and C NMR data, see Tables 1
+
1
and 2; HRESIMS m/z 455.27709 [M + Na] (calcd for C26
5
H40NaO ,
8
9
4.09, brs
5.64, d (5.6)
5.02, brs
4.82, brs
1.83, s
4
55.27680).
5.78, brs
5.01, brs
5.79, brs
5.79, brs
5.0, brs
2
D
ν
5
Altiloxin C (10): White hydrate crystals; [
α
]
ꢀ 27 (c 0.31, MeOH);
1
2
5.0, brs
4
.83, brs
4.82, brs
4.82, brs
1.74, s
UV (MeOH) λmax (log
ε
): 220 (3.42) nm; IR (KBr)
max: 3468, 3414, 2931,
ꢀ
1
1
13
1
1
1
2
3
3
1.74, s
1.74, s
1728, 1700, 1382, 1276, 1246 cm ; H and C NMR data, see Tables 2
4
0.96, d (6.6)
1.20, s
0.96, d (6.7)
1.23, s
0.96, d (6.7)
1.23, s
0.92, d (6.7)
1.0, s
ꢀ
and 3; HRESIMS m/z 303.13731 [Mꢀ H] (calcd for C15
4
H24ClO ,
5
′
303.13686).
2.67, quint (7.0)
4.44, m
2.58, quint (7.2)
4.25, dt (5.0,
2.58, quint (7.2)
4.24, dt (5.3,
7.2)
2.58, quint (7.1)
4.23, brt (7.1)
′
′
′
′
′
′
′
25
D
Altiloxin D (11): White solid; [
α
]
ꢀ 65 (c 0.85, MeOH); UV (MeOH)
7
.2)
λ
1
max (log
ε
): 220 (3.86) nm; IR (KBr) max: 3445, 2962, 1735, 1675,
ν
4
5
6
7
8
9
5.62, dd (6.1,
5.76, dd (5.0,
15.2)
5.81, dd (5.3,
15.2)
5.59, dd (6.8,
15.2)
ꢀ 1
1
13
363, 1256, 1218 cm
;
H and C NMR data, see Tables 2 and 3;
1
5.2)
6.28, dd (10.3,
5.2)
6.12, dd (10.3,
5.0)
5.73, td (7.4,
5.0)
2.30, m
.24, m
3.86, qd (6.1,
1.8)
ꢀ
HRESIMS m/z 267.16018 [Mꢀ H] (calcd for C15
23 4
H O , 267.16018).
5.76, dd (10.3,
15.2)
5.81, dd (10.3,
15.2)
6.26, dd (10.3,
15.2)
2
D
ν
5
1
Altiloxin E (12): White hydrate crystals; [
α]
ꢀ 43 (c 0.52, MeOH);
4.25, dd (10.3,
11.3)
4.20, m
6.12, dd (10.3,
15.1)
UV (MeOH) λmax (log
1733, 1365, 1247 cm
ε
): 220 (3.55) nm; IR (KBr)
max: 3460, 3385, 2912,
1
ꢀ 1
1
13
;
H and C NMR data, see Tables 2 and 3;
4.14, td (6.3,
11.3)
4.14, td (2.8,
6.1)
5.71, td (7.4,
15.1)
+
HRESIMS m/z 275.1618 [M + Na] (calcd for C15
3
H24NaO , 275.1611).
1
25
2.40, m
1.96, m
1.71, m
4.30, m
2.25, m
Phomomane (13): White crystals; [
α
]
ꢀ 47 (c 0.48, MeOH); UV
D
2
1.61, m
(
MeOH) λmax (log
665, 1321, 1227 cm
ε
): 220 (3.65) nm; IR (KBr) max: 3458, 2956, 1726,
ν
4.22, m
3.85, qd (6.2,
12.0)
ꢀ 1
1
13
1
;
H and C NMR data, see Tables 2 and 3;
1
ꢀ
′
′
HRESIMS m/z 253.18128 [Mꢀ H] (calcd for C15
25 3
H O , 253.18092).
1
1
0
1
1.23, d (6.1)
1.22, d (7.2)
1.33, d (6.2)
1.20, d (7.2)
1.30, d (6.0)
1.20, d (7.2)
1.20, d (6.2)
1.18, d (7.2)
2
.3. X-ray crystallographic analysis of compounds 10, 12 and 13
Thereafter, the broth was extracted with EtOAc three times, and the
mycelia was extracted with MeOH twice. Both of the organic phases
were combined and evaporated under reduced pressure to yield the
extracts of 30.5 g. Then, the residue was fractionated by silica gel col-
umn chromatography with a gradient of petroleum ether/EtOAc from
Single crystals of 10, 12 and 13 were obtained from MeOH solution.
The data obtained on an Agilent Xcalibur Nova singlecrystal diffrac-
tometer using Cu k
α
radiation (λ = 1.5418 Å). The structures were
solved by direct methods using SHELXS-97 software and refined with
SHELXS-97 using by full-matrix least-squares, with anisotropic
displacement parameters for all the non-hydrogen atoms. The crystal-
lographic data can be obtained free of charge from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK
1
0:0 to 0:10 to give ten fractions (Fr.1- Fr.10). Fr.2 (2.3 g) was subjected
to silica gel CC (CH Cl /MeOH v/v, 98:2) to yield compound 8 (3.6 mg).
Fr.3 was subjected to silica gel CC (CH Cl /MeOH v/v, 97:3) to yield
compound 9 (3.3 mg) and an additional Fr.3.1 which was purified by
semipreparative reversed-phase HPLC (MeOH-H O, 75:25) to yield
compounds 4 (2.6 mg) and 5 (3.0 mg). Fr.4 was subjected to silica gel CC
CH Cl /MeOH v/v, 88:12) to yield compound 7 (3.3 mg). Fr.5 (5 g) was
purified by Sephadex LH-20 CC (CH Cl /MeOH v/v, 1:1) to afford two
fractions (Fr.5.1 and 5.2). Fr.5.1 was subjected to silica gel CC (CH Cl
MeOH v/v, 91:9) to give compounds 1 (35.5 mg) and 6 (2.3 mg). Fr.5.2
was subjected to silica gel CC (CH Cl /MeOH v/v, 89:11) to yield
compound 2 (3.7 mg) and an additional fraction Fr.5.2.1 which was
purified by Sephadex LH-20 CC (CH Cl /MeOH v/v, 1:1) to give com-
pound 10 (6.8 mg). Fr.6 (45.3 g) was purified by Sephadex LH-20 CC
CH Cl /MeOH v/v, 1:1) to obtain three fractions (Fr.6.1- Fr.6.3). Fr.6.1
was subjected to silica gel CC (CH Cl /MeOH v/v, 83:17) to yield
compound 3 (5.0 mg). Fr.6.2 was subjected to silica gel CC (CH Cl
MeOH v/v, 82:18) to yield compound 11 (3.5 mg). Fr.7 was applied to
silica gel CC (CH Cl /MeOH v/v, 82:18) to give compound 13 (4.0 mg)
and an additional fraction Fr.7.1 which was purified by semipreparative
2
2
2
2
2
(
fax: 44-(0)1223-336033; e-mail: deposit@ccdc.cam.ac.uk).
Crystal data of 10: C15
H
25ClO
4
⋅H
2
O, M
r
= 322.1, monoclinic,
α
=
(
2
2
◦
◦
7
.6804(2) Å, b = 9.4260(3) Å, c = 10.9238(2) Å,
α
= 90.00 , β = 96.90 ,
◦
3
2
2
γ = 90.00 , V = 788.09(4) Å , space group P2
1
, Z = 2, T = 293(2) K,
3
ꢀ 1
3
2
2
/
D
calcd = 1.360 g/cm ,
μ
= 2.316 mm , and F(000) = 348.0. Crystal
dimension: 0.25 × 0.15 × 0.10 mm . Independent reflections: 3077
2
2
(
(
R
int = 0.0395). The final R
values were 0.0634, wR
= 0.1566 (I> = 2σ
1
2
2
I)). The goodness of fit on F was 1.080. Flack parameter = ꢀ 0.03(2).
2
2
CCDC number: 1977144.
Crystal data of 12: C15
H
24
O
3
, M
r
= 252.1, monoclinic,
α
= 6.3767(2)
(
2
2
◦
◦
Å, b = 7.2885(2) Å, c = 16.8669(6) Å,
α
= 80.903 , β = 79.880(10) , γ =
◦
3
2
2
6
1
0
0
6.813 , V = 705.95(4) Å , space group P1, Z = 1, T = 150 K, Dcalcd
=
3
ꢀ 1
2
2
/
.187 g/cm ,
.30 × 0.15 × 0.02 mm . Independent reflections: 24,488 (Rint
.0560). The final R values were 0.0945, wR (I)).
μ
= 0.645 mm , and F(000) = 276.0. Crystal dimension:
3
=
2
2
= 0.3005 (I> = 2σ
1
2
2
The goddess of fit on F was 1.129. Flack parameter = ꢀ 0.04(16). CCDC
reversed-phase HPLC (MeOH-H
mg).
2
O, 70:30) to obtain compound 12 (3.5
number: 1977147.
Crystal data of 13: C15
H
28
O
4
, M
r
= 254.1, monoclinic, α = 6.1447(3)
2