Marmesin

Marmesin
Names
Preferred IUPAC name
(2S)-2-(2-Hydroxypropan-2-yl)-2,3-dihydro-7H-furo[3,2-g][1]benzopyran-7-one
Other names
Nodakenetin
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
UNII
  • InChI=1S/C14H14O4/c1-14(2,

    16)12-6-9-5-8-3-4-13(15)18-10(8)7-11(9)17-12/h3-5,7,12,16H,6H2,

    1-2H3/t12-/m0/s1
    Key: FWYSBEAFFPBAQU-LBPRGKRZSA-N
  • CC(C)([C@@H]1CC2=C(O1)C=C3C(=C2)C=CC(=O)O3)O
Properties
C14H14O4
Molar mass 246.262 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Marmesin (nodakenetin) is a chemical compound precursor in psoralen and linear furanocoumarins biosynthesis.

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

Spectra

IR Spectra

IR (ATR): νmax 3480, 2971, 1699, 1631, 1488 cm-1.

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.

UV-Vis

UV: [neutral]λmax  217 (ε7420); 338 (ε17700)( MeOH)   [neutral]λmax  332( EtOH).

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.

Metabolism in plants

(+)-Marmesin is converted to psoralen by the enzyme psoralen synthase.

2D representation of the chemical structure of marmesin.
(+)-marmesin
 
O2
2 H2O
Rightward reaction arrow with minor substrate(s) from top left and minor product(s) to top right
 
 
 
2D representation of the chemical structure of psoralen .
psoralen
+
 
2D representation of the chemical structure of acetone.
acetone

This is part of the pathway to a group of natural products called furanocoumarins.

References

  1. ↑ 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.
  2. ↑ Chatterjee, A. et al, J. Am. Chem. Soc., 1949, 71, 606-609
  3. ↑ 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.
  4. ↑ 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.
  5. ↑ Anonymous Dictionary of natural products; Chapman & Hall: London, 1994.
  6. ↑ 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.
  7. ↑ 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.
  8. ↑ Dewick, P.M. (2009). Medicinal Natural Products: A Biosynthetic Approach (3rd ed.). Wiley. pp. 164–5. ISBN 978-0-471-49641-0.