Supporting Information
Cadinane-Type Sesquiterpenoids from Heterotheca Inuloides. Absolute Configuration and Anti-inflammatory Activity
Verónica Egas,† Rubén A. Toscano,† Edelmira Linares,‡ Robert Bye,‡ Francisco J. Espinosa-García,§ and Guillermo Delgado*,†
†
Instituto de Química and ‡Instituto de Biología, Universidad Nacional Autónoma de
México, Circuito Exterior, Ciudad Universitaria, Coyoacán 04510, Mexico City, Mexico §
Instituto de Investigaciones en Ecosistemas y Sustentabilidad, Universidad Nacional
Autónoma de México, Antigua carretera a Pátzcuaro No. 8701, Col. Ex-Hacienda de San José de la Huerta, 58190 Morelia, Michoacán, Mexico
Table of contents
S1. 1H NMR spectrum (400 MHz, CDCl3) of compound 1 ................................................... 1 S2. 13C NMR spectrum (100 MHz, CDCl3) of compound 1 .................................................. 2 S3. COSY spectrum (CDCl3) of compound 1 ........................................................................ 3 S4. HSQC spectrum (CDCl3) of compound 1 ........................................................................ 4 S5. HMBC spectrum (CDCl3) of compound 1 ....................................................................... 5 S6. NOESY spectrum (CDCl3) of compound 1 ..................................................................... 6 S7. 1H NMR spectrum (400 MHz, CDCl3) of compound 2 ................................................... 7 S8. 13C NMR spectrum (100 MHz, CDCl3) of compound 2 .................................................. 8 S9. COSY spectrum (CDCl3) of compound 2 ........................................................................ 9 S10. HSQC spectrum (CDCl3) of compound 2 .................................................................... 10 S11. HMBC spectrum (CDCl3) of compound 2 ................................................................... 11 S12. NOESY spectrum (CDCl3) of compound 2 ................................................................. 12 S13. 1H NMR spectrum (400 MHz, CDCl3) of compound 3 ............................................... 13 S14. 13C NMR spectrum (100 MHz, CDCl3) of compound 3 .............................................. 14 S15. COSY spectrum (CDCl3) of compound 3 .................................................................... 15 S16. HSQC spectrum (CDCl3) of compound 3 .................................................................... 16 S17. HMBC spectrum (CDCl3) of compound 3 ................................................................... 17 S18. NOESY spectrum (CDCl3) of compound 3 ................................................................. 18 S19. 1H NMR spectrum (400 MHz, CDCl3) of compound 4 ............................................... 19 S20. 13C NMR spectrum (100 MHz, CDCl3) of compound 4 .............................................. 20 S21. COSY spectrum (CDCl3) of compound 4 .................................................................... 21 S22. HSQC spectrum (CDCl3) of compound 4 .................................................................... 22 S23. HMBC spectrum (CDCl3) of compound 4 ................................................................... 23 S24. NOESY spectrum (CDCl3) of compound 4 ................................................................. 24 S25. 1H NMR spectrum [400 MHz, (CD3)2CO] of compound 4 obtained from dehydration of compound 5 ...................................................................................................................... 25 S26. Experimental and calculated ECD spectra of (-)-3-hydroxy-α-calacorene…….……..26 S27. Comparison of the experimental ECD spectra of natural product 4 and the dehydration product from 5….…….…………………………………………………………………….27
6.54 1.19
1.43 1.42
2.50
7.42 7.40 7.26
7.98 7.86 7.85
9.14
10.17
3.09
CDCl3
3.80
HO
1.04
1.02
1.01 1.00
1.00
0.99
CHO
S1. 1H NMR spectrum (400 MHz, CDCl3) of compound 1.
1
17.2
23.6
29.5
108.0
118.7
131.6 127.8 127.1 125.4
156.8 153.6
195.1
139.2
CDCl3 CHO HO
S2. 13C NMR spectrum (100 MHz, CDCl3) of compound 1.
2
CHO HO
S3. COSY spectrum (CDCl3) of compound 1.
3
CHO HO
S4. HSQC spectrum (CDCl3) of compound 1.
4
CHO HO
S5. HMBC spectrum (CDCl3) of compound 1.
5
CHO HO
S6. NOESY spectrum (CDCl3) of compound 1.
6
O C HO
H
CDCl3
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0 4.5 f1 (ppm)
4.0
3.5
3.0
2.5
2.0
1.5
1.0
S7. 1H NMR spectrum (400 MHz, CDCl3) of compound 2.
7
O C HO
H
CDCl3
S8. 13C NMR spectrum (100 MHz, CDCl3) of compound 2.
8
O C HO
H
S9. COSY spectrum (CDCl3) of compound 2.
9
O C HO
H
S10. HSQC spectrum (CDCl3) of compound 2.
10
O C HO
H
S11. HMBC spectrum (CDCl3) of compound 2.
11
O C HO
H
S12. NOESY spectrum (CDCl3) of compound 2.
12
2.86
2.23 2.06 1.82 1.66
1.01
1.05 2.35 3.15 1.07
6.58 0.29
0.95 0.94 0.91 0.89
3.04
2.01
0.31
5.71 5.62
7.30 7.26
1.00 0.99
1.07
CDCl3
S13. 1H NMR spectrum (400 MHz, CDCl3) of compound 3.
13
S14. 13C NMR spectrum (100 MHz, CDCl3) of compound 3.
14
26.6 26.0 25.5 21.0 19.5 15.1
38.7
44.4
116.9
135.4 132.0 127.5 125.8
140.8
172.1
S15. COSY spectrum (CDCl3) of compound 3.
15
S16. HSQC spectrum (CDCl3) of compound 3. 16
S17. HMBC spectrum (CDCl3) of compound 3. 17
S18. NOESY spectrum (CDCl3) of compound 3.
18
0.91 0.90 0.82 0.80
2.06 1.93 1.91
2.48 2.42 8.0
7.5
6.5
6.0
5.5
5.0 4.5 f1 (ppm)
4.0
3.5
3.0
2.0
1.5
1.53 4.25 3.05
2.5
15.92
1.02
0.55
1.38
0.94
7.0
3.67 1.26 1.10 2.57
8.5
1.25 2.05
9.0
1.05
1.00 0.94
CDCl3
1.0
0.5
S19. 1H NMR spectrum (400 MHz, CDCl3) of compound 4. 19
180
170
160
150
140
130
120
110
100 90 f1 (ppm)
80
70
60
50
40
30
20
10
S20. 13C NMR spectrum (100 MHz, CDCl3) of compound 4.
20
S21. COSY spectrum (CDCl3) of compound 4.
21
S22. HSQC spectrum (CDCl3) of compound 4.
22
S23. HMBC spectrum (CDCl3) of compound 4. 23
S24. NOESY spectrum (CDCl3) of compound 4.
24
(CD3)2CO
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5 f1 (ppm)
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
S25. 1H NMR spectrum [400 MHz, (CD3)2CO] of compound 4 obtained from dehydration of compound 5.
25
S26. Experimental and calculated ECD spectra of (-)-3-hydroxy-α-calacorene
26
S27. Comparison of the experimental ECD spectra of natural product 4 and the dehydration product from 5
27
