Further Mulinane and Azorellane Diterpenoids Isolated from Mulinum crassifolium and Azorella compacta
Abstract
:1. Introduction
2. Results and Discussion
2.1. Isolation and Structural Elucidation of the New Diterpenoids
1 | 2 | |||||
---|---|---|---|---|---|---|
Proton | δH mult. (J in Hz) | HMBC (H→C) | NOE | δH mult. (J in Hz) | HMBC (H→C) | NOE |
1α | 1.24 m | C-5, 9 | 1.83 m | - | - | |
1β | 1.84 dd (11.4, 4.7) | - | 1.37 m | - | - | |
2α | 1.97 m | - | 1.79 m | - | - | |
2β | 1.58 m | - | 1.48 m | - | - | |
3α | 1.48 m | - | 1.35 m | C-2, 4, 5, 18, 19 | H-10α | |
4 | 1.54 m | - | 1.45 m | - | - | |
6α | 1.43 m | - | 1.22 m | - | H-10α | |
6β | 1.52 m | - | 2.45 dt (7.2, 4.0) | C-5, 8 | H-7β, Me-19 | |
7α | 2.56 dt (13.3, 3.2) | C-15, 9, 17 | 1.80 dd (13.6, 4.5) | - | - | |
7β | 1.59 m | - | 1.71 dt (14.3, 4.3) | C-8, 9, 15 | H-6β, H-7β, | |
9β | 2.63 m | C-7, 15, 10, 11 | 2.23 m | C-8, 10, 11, 12, 15 | H-11β, H-17β | |
10α | 2.22 m | C-20, 9, 5, 8, 6 | H-1α, H-6α, H-3α | 1.51 m | C-1, 5, 9 | H-6α, H-3α |
11β | - | - | 5.94 br d (2.4) | C-8, 9, 10, 12, 21 | H-9β, H-17β | |
12 | 5.84 br s | C-9, 13, 14 | 6.20 br s | C-9, 13, 14, 16 | H-11, H-16 | |
14 | 5.75 dd (11.3, 3.8) | C-12, 13, 15 | H-17β, H-15β, H-9β | - | - | - |
15α | 261 dd (14.1, 11.3) | C-14, 7, 17, 13 | 2.62 d (12.7) | C-14, 7, 17, 13, 8 | - | |
15β | 1.68 dd (14.1, 3.8) | - | 2.50 d (12.7) | - | - | |
16 | 1.85 br s | C-13, 12, 14 | 1.87 br s | C-13, 12, 14 | - | |
17α | 3.85 d (11.3) | C-9, 7, 15 | 3.94 d (11.1) | C-8, 9, 15 | - | |
17β | 4.17 d (11.3) | - | H-14β, H-15β | 4.00 d (11.1) | - | H-9β, H-11β |
18 | 0.85 d (5.5) | C-4, 3 | 1.99 d (6.3) | C-4, 3 | - | |
19 | 1.02 d (5.5) | C-4, 3 | 0.82 d (6.3) | C-4, 3 | - | |
22 | 2.11 s | C-21, 14 | 2.09 s | - | - | |
24 | 1.99 s | C-23, 17 | 2.04 s | C-23, 17 | - |
C# | 1 | 2 | C# | 1 | 2 |
---|---|---|---|---|---|
1 | 24.2 t | 25.7 t | 13 | 150.5 s | 138.1 s |
2 | 28.4 t | 28.5 t | 14 | 71.5 d | 201.7 s |
3 | 57.5 d | 57.3 d | 15 | 36.2 t | 52.5 t |
4 | 31.6 d | 31.6 d | 16 | 28.4 q | 18.5 q |
5 | 57.0 s | 56.1 s | 17 | 71.6 t | 71.0 t |
6 | 31.6 t | 32.7 t | 18 | 22.7 q | 22.6 q |
7 | 36.0 t | 34.3 t | 19 | 22.3 q | 22.3 q |
8 | 46.8 s | 37.9 s | 20 | 178.4 s | 178.1 s |
9 | 57.4 d | 45.9 d | 21 | 170.5 s | 170.7 s |
10 | 46.9 d | 47.3 d | 22 | 20.9 q | 21.2 q |
11 | 202.6 s | 72.2 d | 23 | 169.5 s | 169.9 s |
12 | 127.1 d | 139.2 d | 24 | 20.5 q | 20.8 q |
2.2. Semisynthetic Procedures and Proposed Mechanisms of Reaction
2.2.1. Semi-Synthesis of Compounds 1 and 2
2.2.2. Computational Analyses and Mechanism of Reaction
2.2.3. Semi-Synthesis of Compound 3
3. Experimental
3.1. General Experimental Procedures
3.2. Plant Material
3.3. Extraction and Isolation
3.4. Semisynthesis of 14α,17-Diacetoxymulin-12-ene-11-one-20-oic acid (1) and 11α,17-Diacetoxy-mulin-12-en-14-one-20-oic Acid (2)
4. Conclusions
Supplementary Materials
Acknowledgments
Conflicts of Interest
References
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Bórquez, J.; Ardiles, A.; Loyola, L.A.; Peña-Rodriguez, L.M.; Molina-Salinas, G.M.; Vallejos, J.; Collado, I.G.; Simirgiotis, M.J. Further Mulinane and Azorellane Diterpenoids Isolated from Mulinum crassifolium and Azorella compacta. Molecules 2014, 19, 3898-3908. https://doi.org/10.3390/molecules19043898
Bórquez J, Ardiles A, Loyola LA, Peña-Rodriguez LM, Molina-Salinas GM, Vallejos J, Collado IG, Simirgiotis MJ. Further Mulinane and Azorellane Diterpenoids Isolated from Mulinum crassifolium and Azorella compacta. Molecules. 2014; 19(4):3898-3908. https://doi.org/10.3390/molecules19043898
Chicago/Turabian StyleBórquez, Jorge, Alejandro Ardiles, Luis Alberto Loyola, Luis Manuel Peña-Rodriguez, Gloria María Molina-Salinas, Javier Vallejos, Isidro G. Collado, and Mario J. Simirgiotis. 2014. "Further Mulinane and Azorellane Diterpenoids Isolated from Mulinum crassifolium and Azorella compacta" Molecules 19, no. 4: 3898-3908. https://doi.org/10.3390/molecules19043898