Abstract
The purification of fomacta-1(15),4,8-triene is crucial due to its biological significance as a key intermediate in metabolic pathways and its potential applications in pharmacological research. This compound presents a challenge for isolation due to the complexity of the mixtures generated during its production. The objective of this work was to develop an efficient method to purify it and improve the quality of its nuclear magnetic resonance (NMR) spectrum. Initially, verticillol or 12-epi-verticillol was reacted with BF3, yielding a mixture that could not be satisfactorily separated using conventional silica gel. To overcome this limitation, silica gel impregnated with silver nitrate was employed, optimizing the separation process. This method resulted in significantly improved purification, yielding a cleaner and more precise NMR spectrum. These findings highlight the utility of this strategy in purifying complex compounds with biological relevance and therapeutic potential.
References
Chow, S. Y., Williams, H. J., Pennington, J. D., Nanda, S., Reibenspies, J. H., & Scott, A. I. (2007). Studies on taxadiene synthase: interception of the cyclization cascade at the verticillene stage and rearrangement to phomactatriene. Tetrahedron, 63(27), 6204-6209. https://doi.org/10.1016/j.tet.2007.03.029
Damyanova, B., Momtchilova, S., Bakalova, S., Zuilhof, H., Christie, W. W., & Kaneti, J. (2002). Computational probes into the conceptual basis of silver ion chromatography: I. Silver(I) ion complexes of unsaturated fatty acids and esters. Journal of Molecular Structure: THEOCHEM, 589–590, 239–249. https://doi.org/10.1016/S0166-1280(02)00281-6
Daramwar, P. P., Srivastava, P. L., Priyadarshini, B., & Thulasiram, H. V. (2012). Preparative separation of α- and β-santalenes and (Z)-α- and (Z)-β-santalols using silver nitrate-impregnated silica gel medium pressure liquid chromatography and analysis of sandalwood oil. Analyst, 137(19), 4564–4570. https://doi.org/10.1039/C2AN35575B
Del Río-Chávez, Á. A., García-Gutiérrez, H. A., Román-Marín, L. U., Beiza-Granados, L., Cerda-García-Rojas, C. M., Joseph-Nathan, P., & Hernández-Hernández, J. D. (2019). Absolute configuration of phomactatriene diterpenoids obtained by Wagner–Meerwein rearrangement of epimeric verticillols. Chirality, 31(12), 1–13. https://doi.org/10.1002/chir.23061
Drugkar, K., Rathod, W., Sharma, T., Sharma, A., Joshi, J., Pareek, V. K., Ledwani, L., & Diwekar, U. (2021). Advanced separation strategies for up-gradation of bio-oil into value-added chemicals: A comprehensive review. Separation and Purification Technology, 283, 120149.
https://doi.org/10.1016/j.seppur.2021.120149
Goldring, W. P. D., & Pattenden, G. (2006). The Phomactins. A Novel Group of Terpenoid Platelet Activating Factor Antagonists Related Biogenetically to the Taxanes. Accounts Of Chemical Research, 39(5), 354-361. https://doi.org/10.1021/ar050186c
Hammerschick, T., & Vetter, W. (2023). Silver ion chromatography enables the separation of 2‑methylalkylresorcinols from alkylresorcinols. Journal of Separation Science, 46(20), e2300243. https://doi.org/10.1002/jssc.202300243
Hernández-Hernández, J. D., Román-Marín, L. U., Cerda-García-Rojas, C. M., & Joseph-Nathan, P. (2005). Verticillane Derivatives from Bursera suntui and Bursera kerberi. Journal Of Natural Products, 68(11), 1598-1602. https://doi.org/10.1021/np050323e
Kuroda, Y., Nicacio, K. J., Da Silva-Jr, I. A., Leger, P. R., Chang, S., Gubiani, J. R., Deflon, V. M., Nagashima, N., Rode, A., Blackford, K., Ferreira, A. G., Sette, L. D., Williams, D. E., Andersen, R. J., Jancar, S., Berlinck, R. G. S., & Sarpong, R. (2018). Isolation, synthesis and bioactivity studies of phomactin terpenoids. Nature Chemistry, 10(9), 938-945. https://doi.org/10.1038/s41557-018-0084-x
Li, T.-S., Li, J.-T., & Li, H.-Z. (1995). Modified and convenient preparation of silica impregnated with silver nitrate and its application to the separation of steroids and triterpenes. Journal of Chromatography A, 715, 372–375. https://doi.org/10.1016/0021-9673(95)00619-X
Liao, S., Dillon, J. T., Huang, C., Santos, E., & Huang, Y. (2021). Silver (I)-dimercaptotriazine functionalized silica: A highly selective liquid chromatography stationary phase targeting unsaturated molecules. Journal of Chromatography A, 1645, 462122. https://doi.org/10.1016/j.chroma.2021.462122
Morita, M., Mihashi, S., Itokawa, H., & Hara, S. (1983). Silver nitrate impregnation of preparative silica gel columns for liquid chromatography. Analytical Chemistry, 55(2), 412–414. https://doi.org/10.1021/ac00253a065
Niu, T., Yu, J., Wang, Z., Wang, C., Guo, Y., Li, J., & Wang, X. (2024). Purification of triterpenoid saponins and 25R/25S‐inokosterone from Achyranthes bidentata Bl. by high‐speed countercurrent chromatography coupled silver nitrate coordination. Journal Of Separation Science, 47(7). https://doi.org/10.1002/jssc.202300901
Palframan, M. J., & Pattenden, G. (2019). The verticillenes: Pivotal intermediates in the biosynthesis of the taxanes and the phomactins. Natural Product Reports, 36(1), 108–121. https://doi.org/10.1039/c8np00034d
Roth, G. A., Mensah, G. A., & Fuster, V. (2020). The global burden of cardiovascular diseases and risks: A compass for global action. Journal of the American College of Cardiology, 76(25), 2980–2981. https://doi.org/10.1016/j.jacc.2020.11.010
Tokiwano, T., Fukushi, E., Endo, T., & Oikawa, H. (2004). Biosynthesis of phomactins: common intermediate phomactatriene and taxadieneElectronic supplementary information (ESI) available: 1H and 13C NMR spectra for labelled and unlabelled 1.See http://www.rsc.org/suppdata/cc/b4/b401377h/. Chemical Communications, 11, 1324. https://doi.org/10.1039/b401377h
Tryon‑Tasson, N., Ryoo, D., Eor, P., & Anderson, J. L. (2023). Silver‑mediated separations: A comprehensive review on advancements of argentation chromatography, facilitated transport membranes, and solid‑phase extraction techniques and their applications. Journal of Chromatography A, 1705, 464133. https://doi.org/10.1016/j.chroma.2023.464133
Tsujikawa, K., Okada, Y., Segawa, H., Yamamuro, T., Kuwayama, K., Kanamori, T., & Iwata, Y. T. (2022). Thin-layer chromatography on silver nitrate-impregnated silica gel for analysis of homemade tetrahydrocannabinol mixtures. Forensic Toxicology, 40(1), 125–131. https://doi.org/10.1007/s11419-021-00592-9
Williams, C. M., & Mander, L. N. (2001). Chromatography with silver nitrate. Tetrahedron, 57(3), 425-447. https://doi.org/10.1016/s0040-4020(00)00927-3
Yin, Z., & Dickschat, J. S. (2023). Engineering fungal terpene biosynthesis. Natural Product Reports, 40(1), 28–45. https://doi.org/10.1039/D2NP00020B
Zhang, L., Zhang, B., Zhu, A., Liu, S. H., Wu, R., Zhang, X., Xu, Z., Tan, R. X., & Ge, H. M. (2023). Biosynthesis of Phomactin platelet activating factor antagonist requires a two-enzyme cascade. Angewandte Chemie International Edition, 62(47), e202312996. https://doi.org/10.1002/anie.202312996
Zhang, Q., Lin, L., & Ye, W. (2018). Techniques for extraction and isolation of natural products: a comprehensive review. Chinese Medicine, 13(1). https://doi.org/10.1186/s13020-018-0177-x
Zhang, W.-M., Zhai, Y.-C., Yang, H.-J., Zhang, R.-G., Hao, J., Han, J.-Q., & Zhang, Y.-L. (2015). Silver nitrate–silica gel column chromatography purification linolenic acid in walnut oil. Science and Technology of Food Industry, 36(10), 229–232. https://doi.org/10.13386/j.issn1002-0306.2015.10.039
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