Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
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Supplementary Materials: Three Pairs of New
Isopentenyl Dibenzo[b,e]oxepinone Enantiomers
from Talaromyces flavus, a Wetland
Soil-Derived Fungus
Tian-Yu Sun, Run-Qiao Kuang, Guo-Dong Chen, Sheng-Ying Qin, Chuan-Xi Wang, Dan Hu,
Bing Wu, Xing-Zhong Liu, Xin-Sheng Yao, Hao Gao
Table S1. 1D and 2D data of 1 (1H for 400 MHz, 13C for 100 MHz in CDCl3).
Position
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1′
2′
3′
4′
5′
OCH3
10-OH
14-OH
δC, Type
21.8, CH3
147.1, C
116.8, CH
138.5, C
103.4, CH
154.5, C
109.3, CH
137.6, CH
124.8, C
162.8, C
113.6, C
197.5, C
116.8, C
162.4, C
119.5, CH
27.8, CH2
121.8, CH
133.2, C
25.8, CH3
17.8, CH3
56.9, CH3
δH (J in Hz)
2.37, s
H-1H COSY
1
HMBC
2, 3, 15
6.94, s
1, 5, 13, 15
5.64, s
3, 6, 13, OCH3
6.58, d (8.3)
7.33, d (8.3)
8
7
6, 9, 11
6, 10, 1′
6.87, s
3.34, d (7.3)
5.33, br t (7.3)
2′
1′, 4′, 5′
1, 3, 13, 14
8, 9, 10, 2′, 3′
1′, 4′, 5′
1.77, br s
1.73, br s
3.57, s
13.62, s
11.46, s
2′
2′
2′, 3′, 5′
2′, 3′, 4′
5
9, 10, 11
13, 14, 15
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
4'
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1'
5'
O
OH
2'
9
15
13
11
8
HO
1
2
6
4
O 5
1''
O
2''
2
Table S2. 1D and 2D data of 2 (1H for 600 MHz, 13C for 150 MHz in CDCl3).
Position
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1′
δC, Type
21.9, CH3
147.2, C
116.8, CH
138.8, C
102.0, CH
154.8, C
109.3, CH
137.6, CH
124.7, C
162.7, C
113.7, C
197.6, C
116.9, C
162.3, C
119.4, CH
27.8, CH2
2′
3′
4′
5′
1′′
121.8, CH
133.3, C
25.8, CH3
17.8, CH3
65.3, CH2
2′′
10-OH
14-OH
14.8, CH3
δH (J in Hz) a
2.38, s
H-1H COSY
1
HMBC
2, 3, 15
6.98, s
1, 5, 13, 15
5.74, s
3, 6, 13, 1′′
6.55, d (8.3)
7.32, d (8.3)
8
7
6, 9, 11
6, 10, 1′
6.86, s
3.35, dd (15.9, 7.4), a
3.31, dd (15.9, 7.4), b
5.32
1′b, 2′
1′a, 2′
1′a, 1′b, 4′, 5′
1, 3, 13, 14
8, 9, 10, 2′, 3′
8, 9, 10, 2′, 3′
1′, 4′, 5′
1.76, br s
1.73, br s
3.96, dq (9.6, 7.1), a
3.66, dq (9.6, 7.1), b
1.26, t (7.1)
13.63, s
11.44, s
2′
2′
1′′b, 2′′
1′′a, 2′′
1′′a, 1′′b
2′, 3′, 5′
2′, 3′, 4′
5, 2′′
5, 2′′
1′′
9, 10, 11
13, 14, 15
a: Indiscernible signals owing to overlapping or having complex multiplicity are reported without
designating multiplicity.
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
S3 of S19
OH
6
7
8
2'
4'
9
O
11
HO
15
13
10 O
5
1'
5'
1
2
4
O
3
Table S3. 1D and 2D data of 3 (1H for 400 MHz, 13C for 100 MHz in CDCl3).
Position
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1′
δC, Type
21.9, CH3
147.1, C
116.6, CH
138.3, C
103.9, CH
163.5, C
112.2, CH
138.4, CH
121.8, C
153.2, C
113.9, C
197.5, C
117.0, C
161.9, C
119.4, CH
28.0, CH2
2′
3′
4′
5′
OCH3
6-OH
14-OH
122.1, CH
133.2, C
25.7, CH3
17.8, CH3
57.3, CH3
δH (J in Hz) a
2.39, s
H-1H COSY
1
HMBC
2, 3, 15
6.97, s
1, 5, 13, 15
5.71, s
3, 10, 13, OCH3
6.70, d (8.5)
7.35, d (8.5)
8
7
6, 9, 11
6, 10, 1′
6.87, s
3.36, dd (15.6, 7.5), a
3.30, dd (15.6, 7.5), b
5.25
1′b, 2′
1′a, 2′
1′a, 1′b, 4′, 5′
1, 3, 13, 14
8, 9, 10, 2′, 3′
8, 9, 10, 2′, 3′
1′, 4′, 5′
1.73, br s
1.71, br s
3.57, s
13.14, s
11.22, s
2′
2′
2′, 3′, 5′
2′, 3′, 4′
5
6, 7, 11
13, 14, 15
a: Indiscernible signals owing to overlapping or having complex multiplicity are reported without
designating multiplicity.
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
S4 of S19
OH O
6
7
8
9
2'
5'
HO
13
11
15
2
1
4
10 O
5
OH
1'
4'
4
Table S4. 1D and 2D data of 4 (1H for 400 MHz, 13C for 100 MHz in CDCl3).
Position
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1′
δC, Type
22.0, CH3
147.6, C
116.0, CH
139.7, C
97.1, CH
163.6, C
112.9, CH
138.5, CH
122.4, C
154.0, C
114.6, C
197.3, C
116.5, C
163.3, C
119.8, CH
28.9, CH2
2′
3′
4′
5′
6-OH
14-OH
123.1, CH
133.0, C
25.7, CH3
18.0, CH3
δH (J in Hz)
2.40, s
H-1H COSY
1
HMBC
2, 3, 15
7.07, s
1, 5, 13, 15
6.11, s
3, 10, 13
6.71, d (8.4)
7.34, d (8.4)
8
7
6.89, s
3.36, dd (15.4, 7.2), a
3.22, dd (15.4, 7.2), b
5.24, br t (7.2)
1′b, 2′
1′a, 2′
1′a, 1′b, 4′,5′
1.76, s
1.74, s
12.95, br s
11.82, br s
2′
2′
9, 11
6, 10, 1′
1, 3, 13
8, 9, 2′, 3′
5′
2′, 3′, 5′
2′, 3′, 4′
6, 7, 11
13, 14, 15
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
4'
O
OH
1'
5'
S5 of S19
2'
9
8
HO
15
13
11
2
6
1
4
O 5
OH
5
Table S5. 1D and 2D data of 5 (1H for 400 MHz, 13C for 100 MHz in CDCl3).
Position
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1′
2′
3′
4′
5′
10-OH
14-OH
δC, Type
21.9, CH3
147.4, C
116.2, CH
139.3, C
96.6, CH
154.5, C
109.6, CH
137.7, CH
125.1, C
162.9, C
113.5, C
197.3, C
116.7, C
162.7, C
119.7, CH
27.8, CH2
121.7, CH
133.4, C
25.8, CH3
17.8, CH3
δH (J in Hz)
2.40, s
H-1H COSY
1
HMBC
2, 3, 15
7.04, s
1, 5, 13, 15
6.12, s
3, 6, 13
6.53, d (8.4)
7.32, d (8.4)
8
7
6, 9, 11
6, 10, 1′
6.89, s
3.33, d (7.5)
5.31, br t (7.5)
2′
1′, 4′, 5′
1, 3, 13
8, 9, 10, 2′, 3′
4′, 5′
1.76, s
1.72, s
13.61, br s
11.54, br s
2′
2′
2′, 3′, 5′
2′, 3′, 4′
9, 10, 11
13, 14, 15
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
S6 of S19
HPLC Analyses of 2 and 3
mAU
208nm,4nm (1.00)
500
400
300
200
100
0
0
mAU
208nm,4nm (1.00)
10
20
30
40
min
400
300
200
100
0
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
min
Figure S1. HPLC analysis of 2 (a: the analysis of 2 on routine ODS HPLC; b: the analysis of 2 on
chiral HPLC).
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
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mAU
208nm,4nm (1.00)
1000
750
500
250
0
0
10
mAU
208nm,4nm (1.00)
20
30
40
min
2250
2000
1750
1500
1250
1000
750
500
250
0
-250
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
25.0
27.5
30.0
32.5
35.0
37.5
min
Figure S2. HPLC analysis of 3 (a: the analysis of 3 on routine ODS HPLC; b: the analysis of 3 on
chiral HPLC).
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
S8 of S19
Quantum Chemical ECD Calculations of 1 and 3
Table S6. Conformers distribution of (5S)-1 in solvated models calculations at the APFD/6-31G(d).
Conformers
1
2
3
4
5
6
7
8
Contribution %
27.49
26.71
15.38
15.35
4.77
4.68
2.83
2.79
Figure S3. Most stable conformers of (5S)-1.
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
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Table S7. Conformers distribution of (5S)-3 in solvated models calculations at the APFD/6-31G(d).
Conformers
1
2
3
4
5
6
Contribution %
74.24
13.36
7.20
1.87
1.68
1.66
Figure S4. Most stable conformers of (5S)-3.
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
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The 1D and 2D NMR Spectra of 1−5
230
220
210
200
190
180
170
160
150
140
130
120
110
f1 (ppm)
100
90
80
70
60
27.78
25.77
21.78
17.75
56.89
77.32
77.00
76.68
138.46
137.57
133.22
124.84
121.81
119.48
116.84
113.62
109.26
103.40
162.75
162.40
154.51
147.12
197.48
Figure S5. 1H-NMR spectrum of compound 1 (400 MHz, in CDCl3).
50
40
30
Figure S6. 13C-NMR spectrum of compound 1 (100 MHz, in CDCl3).
20
10
0
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
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-1.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
9.0
8.0
7.0
6.0
5.0
4.0
f2 (ppm)
3.0
2.0
1.0
0.0
Figure S7. 1H-1H COSY spectrum of compound 1 (in CDCl3).
Figure S8. HSQC spectrum of compound 1 (in CDCl3).
-1.0
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
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15
14
13
12
11
10
9
8
f1 (ppm)
7
6
5
3
1.76
1.73
1.26
2.38
3.12
4
3.41
3.18
5.57
3.96
3.96
3.67
3.66
3.33
5.32
1.47
1.00
1.16
2.29
5.74
1.25
1.16
1.04
1.15
1.15
7.33
7.31
6.98
6.86
6.56
6.54
11.44
1.04
1.00
13.63
Figure S9. HMBC spectrum of compound 1 (in CDCl3).
2
Figure S10. 1H-NMR spectrum of compound 2 (600 MHz, in CDCl3).
1
0
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
Figure S11. 13C-NMR spectrum of compound 2 (150 MHz, in CDCl3).
Figure S12. 1H-1H COSY spectrum of compound 2 (in CDCl3).
S13 of S19
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
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Figure S13. HSQC spectrum of compound 2 (in CDCl3).
0
20
40
60
80
100
120
140
160
180
200
14
13
12
11
10
9
8
f2 (ppm)
7
6
5
4
Figure S14. HMBC spectrum of compound 2 (in CDCl3).
3
2
1
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
Figure S15. 1H-NMR spectrum of compound 3 (400 MHz, in CDCl3).
Figure S16. 13C-NMR spectrum of compound 3 (100 MHz, in CDCl3).
S15 of S19
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
Figure S17. 1H-1H COSY spectrum of compound 3 (in CDCl3).
Figure S18. HSQC spectrum of compound 3 (in CDCl3).
S16 of S19
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
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2.40
2.40
1.76
1.74
1.72
3.33
3.32
7.35
7.33
7.31
7.26
7.07
7.04
6.89
6.72
6.70
6.54
6.52
6.12
6.11
5.31
5.24
11.82
11.54
12.95
13.61
Figure S19. HMBC spectrum of compound 3 (in CDCl3).
Figure S20. 1H-NMR spectrum of compounds 4 and 5 (400 MHz, in CDCl3).
210
200
190
180
170
160
150
140
130
S18 of S19
120
110
100
f1 (ppm)
28.87
27.79
25.82
25.73
21.97
21.93
17.95
17.80
123.13
121.71
119.75
119.65
116.18
112.92
109.57
97.05
96.55
139.29
138.47
137.66
164.45
163.61
163.33
162.92
162.67
154.50
154.04
147.60
147.40
197.29
197.26
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
90
80
70
60
50
40
30
Figure S21. 13C-NMR spectrum of compounds 4 and 5 (100 MHz, in CDCl3).
Figure S22. 1H-1H COSY spectrum of compounds 4 and 5 (in CDCl3).
20
10
0
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f1 (ppm)
Molecules 2016, 21, 1184; doi:10.3390/molecules21091184
Figure S23. HSQC spectrum of compounds 4 and 5 (in CDCl3).
0
20
40
60
100
120
140
160
180
200
14
13
12
11
10
9
8
7
f2 (ppm)
6
5
4
3
2
Figure S24. HMBC spectrum of compounds 4 and 5 (in CDCl3).
1
0
f1 (ppm)
80