Marmesin (nodakenetin) is a chemical compound
precursor in
psoralen
Psoralen (also called psoralene) is the parent compound in a family of naturally occurring organic compounds known as the linear furanocoumarins. It is structurally related to coumarin by the addition of a fused furan ring, and may be considered a ...
and linear
furanocoumarin
The furanocoumarins, or furocoumarins, are a class of organic chemical compounds produced by a variety of plants. Most of the plant species found to contain furanocoumarins belong to a handful of plant families. The families Apiaceae and Rutacea ...
s
biosynthesis
Biosynthesis, i.e., chemical synthesis occurring in biological contexts, is a term most often referring to multi-step, enzyme-Catalysis, catalyzed processes where chemical substances absorbed as nutrients (or previously converted through biosynthe ...
.
Marmesin plays a central role in the biosynthesis of furocoumarins in the plant ruta graveolens, more commonly known as rue. It acts as the natural intermediate in the formation of the furan ring that leads to a 4’,5’-dihydro furocoumarin-derivative. This substance can then be transformed into psoralen and other furocoumarins present in rue. Upon feeding the herb a dose of marmesin, radioactivity became strongly incorporated into psoralen and thus the plant itself. It is constituent of ''
Aegle marmelos
''Aegle marmelos'', commonly known as bael (or ''bili'' or ''bhel''), also Bengal quince, golden apple, Japanese bitter orange, stone apple or wood apple, is a species of tree native to the Indian subcontinent and Southeast Asia. It is present i ...
'', ''
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:
eutral�max 217 (ε7420); 338 (ε17700)( MeOH)
eutral�max 332( EtOH).
Production
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.
[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.]
References
External links
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{{coumarin
Furanocoumarins
Terpeno-phenolic compounds