Chemistry:Marmesin
Marmesin (nodakenetin) is a chemical compound precursor in psoralen and linear furanocoumarins biosynthesis.[1]
Marmesin plays a central role in the biosynthesis of furocoumarins in the plant Ruta graveolens, more commonly known as rue. It is the biosynthetic precursor for psoralen and other furocoumarins present in rue. It also a constituent of Aegle marmelos, Ammi majus, Poncirus trifoliata and Prangos bucharica and others [2]
Spectra
IR Spectra
IR (ATR): νmax 3480, 2971, 1699, 1631, 1488 cm-1.[3]
Proton-NMR
1H-NMR (300 MHz, CDCl3): δ 7.59 (d, J = 9.5 Hz, 1H, aromatic), 7.22 (s, 1H, aromatic), 6.75 (d, J = 21.6 Hz, 1H, aromatic), 6.20 (d, J = 9.5 Hz, 1H, aromatic), 4.74 (t, J = 8.8 Hz, 1H, CH), 3.28-3.15 (m, 2H, CH2), 1.87 (s, 1H, OH), 1.37 (s, 3H, CH3), 1.24 (s, 3H, CH3) ppm.[4]
UV-Vis
UV: [neutral]λmax 217 (ε7420); 338 (ε17700)( MeOH) [neutral]λmax 332( EtOH).[5]
Laboratory synthesis
Synthesis of marmesin has been successfully conducted in the laboratory on multiple occasions. One way of doing so is by a strategy based on the palladium-catalyzed intramolecular coupling reaction. This reaction would construct the dihydropyran ring and synthesize the compound from the intermediate (-)-peucedanol. The key step in the overall synthesis uses catalytic asymmetric epoxidation of an enone.[6]
Metabolism in plants
(+)-Marmesin is converted to psoralen by the enzyme psoralen synthase.[7]
- REDIRECT Template:Chemical reaction
This is part of the pathway to a group of natural products called furanocoumarins.[8]
References
- ↑ Steck, Warren; Brown, Stewart A. (1971). "Comparison of (+)- and (−)-Marmesin as Intermediates in the Biosynthesis of Linear Furanoconmarins". Biochemistry and Cell Biology 49 (11): 1213–1216. doi:10.1139/o71-174. ISSN 1208-6002. PMID 5134594.
- ↑ Chatterjee, A. et al, J. Am. Chem. Soc., 1949, 71, 606-609
- ↑ Ando, T.; Nagumo, M.; Ninomiya, M.; Tanaka, K.; Linhardt, R. J.; Koketsu, M. Synthesis of coumarin derivatives and their cytoprotective effects on t-BHP-induced oxidative damage in HepG2 cells. Bioorg. Med. Chem. Lett. 2018, 28, 2422-2425.
- ↑ Kommera, R.; Bhimapaka, C. R. A simple and efficient approach for the preparation of dihydroxanthyletin, xanthyletin, decursinol and marmesin. Synthetic Communications 2020, 50, 3204-3211.
- ↑ Anonymous Dictionary of natural products; Chapman & Hall: London, 1994.
- ↑ Nemoto, T.; Ohshima, T.; Shibasaki, M. Enantioselective total syntheses of novel PKC activator (+)-decursin and its derivatives using catalytic asymmetric epoxidation of an enone. Tetrahedron Lett. 2000, 41, 9569-9574.
- ↑ Larbat, Romain; Kellner, Sandra; Specker, Silvia; Hehn, Alain; Gontier, Eric; Hans, Joachim; Bourgaud, Frederic; Matern, Ulrich (2007). "Molecular Cloning and Functional Characterization of Psoralen Synthase, the First Committed Monooxygenase of Furanocoumarin Biosynthesis". Journal of Biological Chemistry 282 (1): 542–554. doi:10.1074/jbc.M604762200. PMID 17068340. https://hal.science/hal-01738059.
- ↑ Dewick, P.M. (2009). Medicinal Natural Products: A Biosynthetic Approach (3rd ed.). Wiley. pp. 164–5. ISBN 978-0-471-49641-0. https://archive.org/details/medicinalnatural00dewi_458.
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