Supporting Information Chondrosterins A–E，Triquinane-Type Sesquiterpenoids from Soft Coral-Associated Fungus Chondrostereum sp. Hou-Jin Li 1, Ying-Lu Xie 1, Zhong-Liang Xie 2, Ying Chen 1, Chi-Keung Lam 1 and Wen-Jian Lan2, * 1
School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, P. R. China; E-Mails:
[email protected](H.L.);
[email protected](Y.X.);
[email protected](Y.C.);
[email protected](C. L.) 2 School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, P. R. China; E-Mails:
[email protected] (Z.X.);
[email protected] (W.L.) * Author to whom correspondence should be addressed; E-Mail:
[email protected] (W. L.); Tel.: +86-20-39943042; Fax: +86-20-39943000. Table of Contents S1: HREIMS of chondrosterin A (1) S2: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin A (1) S3: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin A (1) S4: gHMQC of chondrosterin A (1) S5: gHMBC of chondrosterin A (1) S6: 1H–1H gCOSY of chondrosterin A (1) S7: ROESY of chondrosterin A (1) S8: HREIMS of chondrosterin B (2)
1
S9: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin B (2) S10: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin B (2) S11: gHMQC of chondrosterin B (2) S12: gHMBC of chondrosterin B (2) S13: 1H NMR (400 MHz, [D6]DMSO) spectrum of chondrosterin B (2) S14: ROESY of chondrosterin B (2) (400 MHz, [D6]DMSO) S15: HREIMS of chondrosterin C (3) S16: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin C (3) S17: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin C (3) S18: gHMQC of chondrosterin C (3) S19: gHMBC of chondrosterin C (3) S20: 1H–1H gCOSY of chondrosterin C (3) S21: NOE of chondrosterin C (3) S22: HREIMS of chondrosterin D (4) S23: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin D (4) S24: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin D (4) S25: gHMQC of chondrosterin D (4) S26: gHMBC of chondrosterin D (4) S27: HREIMS of chondrosterin E (5) S28: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin E (5) S29: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin E (5) S30: gHMQC of chondrosterin E (5) S31: gHMBC of chondrosterin E (5) S32: 1H–1H gCOSY of chondrosterin E (5) S33: ROESY of chondrosterin E (5)
2
Full ms [227.500 - 246.500 ] - Range: 232.000 - 232.500 Scan No. 11 of 15 Scan #: 11 RT: 0.44 Data points: 1 Mass
Theoretical Mass
100.0
Delta [ppm]
232.1458
Delta [mmu]
RDB
-0.7
Instrument:MAT 95XP(Thermo) D:\DATA-HR\11\090802-c1
Composition
-0.2 9/8/2011 4:27:01 PM
6.0
C15
H20
O2
SF2-PD-CC9
090802-c1 #11 RT: 0.44 AV: 1 NL: 1.31E4 T: + c EI Full ms [ 227.50-246.50] 232.1456
100 95 90 85 80 75 70 65 60 Relative Abundance
232.1456
Relative Intensity
55 50 45 40 35 30 25 20 15 10 5 0 231.4
231.6
231.8
232.0
232.2
232.4
232.6
232.8
233.0
m/z
S1: HREIMS of chondrosterin A (1) 3
S2: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin A (1) 4
3.04 3.50 3.03
1.47 0.37 0.28 0.35 0.47 1.38 1.22
1.08
1.07 1.05
1.00
1.00
0.90
-0.012
1.913 1.886 1.761 1.757 1.743 1.739 1.662 1.634 1.626 1.606 1.190 1.140 1.121
2.771 2.741 2.730 2.727 2.700 2.697 2.350 2.331 2.312
5.157
6.022 6.021 5.890
7.260
S3: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin A (1) 5
S4: gHMQC of chondrosterin A (1) 6
S5: gHMBC of chondrosterin A (1) 7
0079COSY-SF2-PD-CC9
1.5
2.0
2.5
3.0
4.0
f1 (ppm)
3.5
4.5
5.0
5.5
6.0
6.4
6.0
5.6
5.2
4.8
4.4
4.0 3.6 f2 (ppm)
3.2
2.8
2.4
2.0
1.6
S6: 1H–1H gCOSY of chondrosterin A (1) 8
1.0 1.5 2.0 3.0 3.5 4.0
f1 (ppm)
2.5
4.5 5.0 5.5 6.0 5.5
4.5
3.5 f2 (ppm)
2.5
1.5
S7: ROESY of chondrosterin A (1) 9
Full ms [239.500 - 258.500 ] - Range: 246.000 - 246.500 Scan No. 16 of 16 Scan #: 16 RT: 0.60 Data points: 1
246.1250
Relative Intensity 77.1
Theoretical Mass
Delta [ppm]
246.1250
Delta [mmu]
RDB
Composition
-0.3
-0.1
Instrument:MAT 95XP(Thermo) D:\DATA-HR\11\090806-c1
9/8/2011 4:40:26 PM
7.0
C15
H18 O3
SF2-PD-CC10-12B
090806-c1 #16 RT: 0.60 AV: 1 NL: 2.44E5 T: + c EI Full ms [ 239.50-258.50] 246.1250
100 95 90 85 80 75 70 65 60 Relative Abundance
Mass
55 50 45 40 35 30 25 20 15 10 5 0 246.02
246.04
246.06
246.08
246.10
246.12 m/z
246.14
246.16
246.18
246.20
246.22
S8: HREIMS of chondrosterin B (2) 10
S9: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin B (2) 11
1.402 1.183 1.166 1.152 1.038
2.99 2.98 3.05 2.96
1.53
2.117 2.089 1.988 1.960
3.011 2.996 2.982 2.968 1.03
1.13
3.468
6.204
1.01
0.82
7.260 7.116 7.115
1.01
S10: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin B (2) 12
S11: gHMQC of chondrosterin B (2) 13
f1 (ppm)
S12: gHMBC of chondrosterin B (2) 14
0.001
3.293 2.898 2.880 2.862 2.844 2.500 2.496 2.491 1.988 1.988 1.907 1.872 1.303 1.194 1.176 1.158 1.086 1.036 1.019 0.943
4.058 4.040 4.023 4.005
5.515
6.201
7.251
28000 26000 24000
EtOAc:4.031,q,J=7.2 Hz,CH2;1.988,s, CH3;1.176, t,J=7.2 Hz, CH3
22000 20000
H2O
18000 16000 14000 12000 10000 8000 6000 4000 2000
7.5
6.5
5.5
4.5
3.5 f1 (ppm)
2.5
1.5
4.60 5.23 3.83
3.67
1.28 8.53 1.46
1.44
14.41
5.08
1.19
1.11
1.00
0 -2000 0.5
S13: 1H NMR (400 MHz, [D6]DMSO) spectrum of chondrosterin B (2) 15
S14: ROESY of chondrosterin B (2) (400 MHz, [D6]DMSO) 16
Full ms [239.500 - 258.500 ] - Range: 248.000 - 248.300 Scan No. 13 of 18 Scan #: 13 RT: 0.51 Data points: 1
248.1405
Relative Intensity Theoretical Mass 100.0
Delta [ppm]
Delta [mmu]
248.1407
-0.9
RDB
Composition
-0.2
Instrument:MAT 95XP(Thermo) D:\DATA-HR\11\090808-c2
9/8/2011 4:46:26 PM
6.0
C15
H20
O3
SF2-CC13-HPLC-B
090808-c2 #13 RT: 0.51 AV: 1 NL: 1.19E5 T: + c EI Full ms [ 239.50-258.50] 248.1405
100 95 90 85 80 75 70 65 60 Relative Abundance
Mass
55 50 45 40 35 30 25 20 15 10 5 0 248.00
248.05
248.10
248.15 m/z
248.20
248.25
S15: HREIMS of chondrosterin C (3) 17
S16: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin C (3) 18
2.72 3.04 2.83 3.00
1.06 0.54 1.13 0.16 0.31 1.10
0.49 0.54 1.03
0.97
1.00
1.173 1.164 1.076 1.053 1.038
2.925 2.922 2.890 2.887 2.884 2.852 2.832 2.818 2.496 2.493 2.459 2.455 2.428 2.426 2.414 2.411 2.400 2.397 2.385 2.383 2.363 2.344 2.324 2.306 2.285
3.465 3.421 3.418
4.812 4.810 4.798 4.796
7.260
S17: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin C (3) 19
f1 (ppm)
S18: gHMQC of chondrosterin C (3) 20
S19: gHMBC of chondrosterin C (3) 21
f1 (ppm)
S20: 1H–1H gCOSY of chondrosterin C (3) 22
S21: NOE of chondrosterin C (3) 23
Full ms [242.100 - 255.700 ] - Range: 242.100 - 255.700 Scan No. 5 of 18 Scan #: 5 RT: 0.24 Data points: 1 Mass 100.0
Delta[ppm] Delta[mmu]
246.1250
RDB
Composition
1.9
Instrument:MAT 95XP(Thermo) D:\DATA-HR\11\101201-sf2-c1
0.5 10/12/2011 3:47:03 PM
7.0
C15
H18
O3
SF2-CC13S
101201-sf2-c1 #5 RT: 0.24 AV: 1 NL: 2.50E5 T: + c EI Full ms [ 242.10-255.70] 246.1255
100 95 90 85 80 75 70 65 60 Relative Abundance
246.1255
Relative Intensity Theoretical Mass
55 50 45 40 35 30 25 20 15 10 5 0 245.5
245.6
245.7
245.8
245.9
246.0
246.1
246.2
246.3
246.4
246.5
246.6
246.7
246.8
m/z
S22: HREIMS of chondrosterin D (4) 24
S23: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin D (4) 25
285c-sf2-ccl3s 21000 20000 19000 18000 17000 16000 15000 14000 13000 12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0
230
220
210
200
190
180
170
160
150
140
130
120
110 100 f1 (ppm)
90
80
70
60
50
40
30
20
10
0
-10
-20
S24: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin D (4) 26
f1 (ppm)
S25: gHMQC of chondrosterin D (4) 27
f1 (ppm)
S26: gHMBC of chondrosterin D (4) 28
Full ms [227.500 - 246.500 ] - Range: 234.000 - 234.500 Scan No. 12 of 14 Scan #: 12 RT: 0.46 Data points: 1
234.1613
Relative Intensity 65.5
Theoretical Mass
Delta[ppm]
Delta[mmu]
234.1614
RDB
Composition
-0.4
Instrument:MAT 95XP(Thermo) D:\DATA-HR\11\090804-c1
-0.1
9/8/2011 4:34:31 PM
5.0
C15
H22
O2
SF2-PD-CC9-HPLC19
090804-c1 #12 RT: 0.46 AV: 1 NL: 3.28E4 T: + c EI Full ms [ 227.50-246.50] 234.1613
100 95 90 85 80 75 70 65 60 Relative Abundance
Mass
55 50 45 40 35 30 25 20 15 10 5 0 233.5
233.6
233.7
233.8
233.9
234.0
234.1
234.2 m/z
234.3
234.4
234.5
234.6
234.7
234.8
S27: HREIMS of chondrosterin E (5) 29
S28: 1H NMR (500 MHz, CDCl3) spectrum of chondrosterin E (5) 30
2.96
3.02
3.01
2.17
2.12
1.25
3.08
1.05
2.10
3.924 3.911
1.02
0.930
1.759 1.744 1.674 1.662 1.648 1.636 1.504 1.479 1.461 1.459 1.350 1.094
2.033 2.031
2.657 2.652 2.645 2.640 2.635 2.627 2.622 2.611 2.609 2.606 2.601 2.591 2.585 2.580 2.573 2.568 2.564 2.552 2.547 2.337 2.332
5.726 5.723 5.721 5.718
1.00
7.260
S29: 13C NMR (125 MHz, CDCl3) spectrum of chondrosterin E (5) 31
f1 (ppm)
S30: gHMQC of chondrosterin E (5) 32
f1 (ppm)
S31: gHMBC of chondrosterin E (5) 33
f1 (ppm)
S32: 1H–1H gCOSY of chondrosterin E (5) 34
1.0
2.0
3.0
4.0
5.0
ppm (t1 5.0
4.0
3.0
2.0
1.0
ppm (t2)
S33: ROESY of chondrosterin E (5) 35
