Norbadione A

Norbadione A is a pigment found in the bay bolete mushroom (Boletus badius). A polyphenol, norbadione A is related to a family of mushroom pigments known as pulvinic acids.^[1] The molecule has also been reported as a potassium salt from the mushrooms Pisolithus tinctorius (horse dung fungus)^[2] and Chalciporus piperatus.^[3]

Norbadione A

Names
Preferred IUPAC name [2(32)E,52(6)E]-14,33,48,53,74-Pentahydroxy-35,42,55-trioxo-35H,42H,55H-4(4,6)-naphtho[1,8-bc]furana-3(2,4),5(4,2)-difurana-1,7(1)-dibenzenaheptaphane-2(32),52(6)-diene-2,6-dicarboxylic acid
Identifiers
CAS Number	90295-68-4
3D model (JSmol)	Interactive image
ChEBI	CHEBI:210651
ChemSpider	28284768
PubChem CID	54679293
UNII	8DH6BNL8BA
CompTox Dashboard (EPA)	DTXSID301045531
InChI InChI=1S/C35H18O15/c36-15-5-1-12(2-6-15)22(31(41)42)29-26(39)21(34(46)49-29)14-9-17-18(11-20(38)28-24(17)19(10-14)33(45)48-28)25-27(40)30(50-35(25)47)23(32(43)44)13-3-7-16(37)8-4-13/h1-11,36-40H,(H,41,42)(H,43,44)/b29-22+,30-23+ Key: NEAFOYGNZAYARY-KBWMUOTDSA-N
SMILES O=C(O)C(\c1ccc(O)cc1)=C7\OC(\O)=C(\c2cc(O)c4OC(=O)c3cc(cc2c34)\C6=C(/O)O\C(=C(/c5ccc(O)cc5)C(=O)O)C6=O)C7=O
Properties
Chemical formula	C35H18O15
Molar mass	678.50842 gmol−1
Appearance	red needles
Density	1.902 g/cm3
Melting point	300 °C (572 °F; 573 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Properties

Norbadione A has seven acid-base functional groups, among which are two enolic and two carboxylic acid moieties.^[4] These functional groups confer water-solubility to the molecule. It selectively complexes caesium cations (Cs⁺),^[5] with an efficiency comparable to that of some calixarenes or crown ethers.^[4] It has been investigated for its ability to provide a protective effect against the damaging effects of ionizing radiation, an effect attributed to its ability to protect DNA-related targets from irradiation.^[6] Tests with cell cultures and mice show that although it has some protective effect, it is toxic to cells in higher doses.^[7] A diverse array of synthetic derivatives of norbadione A has been created to explore the effect of structure on antioxidant properties and cytotoxicity.^[8] A series of alkali chelators based on the structure of norbadione A has been reported.^[9] The intramolecular protonation process has been determined. There is a pH-dependent Z to E isomer switch that occurs in both pulvinate moieties,^[10] which yields four stereoisomeric forms (E/E, E/Z, Z/Z, Z/E). These stereoisomers may have a widely differing ability to form complexes with Cs⁺ in solution.^[6]

Synthesis

Bourdreux and colleagues reported a total synthesis of norbadione A in 2008. The technique uses a regioselective Diels–Alder reaction and a double Suzuki-Miyaura cross-coupling.^[11]

References

1. Aumann DC, Clooth G, Steffan B, Steglich W (1989). "Complexation of cesium-137 by the cap pigments of the bay boletus (Xerocomus badius)". Angewandte Chemie International Edition in English. 28 (4): 453–454. doi:10.1002/anie.198904531.
2. Thompson RH (1997). Naturally Occurring Quinones IV. Springer. p. 282. ISBN 978-0-7514-0248-3.
3. Yannai S. (2013). Dictionary of Food Compounds. CRC Press. p. 1416. ISBN 978-1-4200-8351-4.
4. Korovitch A, Mulon JB, Souchon V, Leray I, Valeur B, Mallinger A, Nadal B, Le Gall T, Lion C, Ha-Duong NT, El Hage Chahine JM (2010). "Norbadione A: kinetics and thermodynamics of cesium uptake in aqueous and alcoholic media". Journal of Physical Chemistry B. 114 (39): 12655–12665. doi:10.1021/jp1060232. PMID 20831226.
5. Kuad P, Schurhammer R, Maechling C, Antheaume C, Mioskowski C, Wipff G, Spiess B (2009). "Complexation of Cs+, K+ and Na+ by norbadione A triggered by the release of a strong hydrogen bond: nature and stability of the complexes". Physical Chemistry Chemical Physics. 11 (44): 10299–10310. Bibcode:2009PCCP...1110299K. doi:10.1039/b912518c. PMID 19890513.
6. Schurhammer R, Diss R, Spiess B, Wipff G (2007). "Conformational and Cs⁺ complexation properties of norbadione-A: A molecular modeling study". Physical Chemistry Chemical Physics. 10 (4): 495–505. doi:10.1039/B712836C. PMID 18183312.
7. Le Roux A, Josset E, Benzina S, Nadal B, Desage-El Murr M, Heurtaux B, Taran F, Denis J-M, Le Gall T, Meunier S, Bischoff P (2012). "Evaluation of the radioprotective potential of the polyphenol norbadione A". Letters in Drug Design & Discovery. 9 (1): 48–53. doi:10.2174/157018012798192900.
8. Habrant D, Poigny S, Ségur-Derai M, Brunel Y, Heurtaux B, Le Gall T, Strehle A, Saladin R, Meunier S, Mioskowski C, Wagner A (2009). "Evaluation of antioxidant properties of monoaromatic derivatives of pulvinic acids". Journal of Medicinal Chemistry. 52 (8): 2454–2464. doi:10.1021/jm801500h. PMID 19309153.
9. Korovitch A, Le Roux A, Barbault F, Hémadi M, Ha-Duong N-T, Lion C, Wagner A, El Hage Chahine J-M (2013). "A new series of Cs⁺, K⁺ and Na⁺ chelators: Synthesis, kinetics, thermodynamics and modeling". Inorganica Chimica Acta. 394: 45–57. doi:10.1016/j.ica.2012.08.009.
10. Kuad P, Borkovec M, Desage-El Murr M, Le Gall T, Mioskowski C, Spiess B (2005). "Inframolecular protonation process of norbadione A: Influence of the ionic environment and stereochemical consequences". Journal of the American Chemical Society. 127 (4): 1323–1333. doi:10.1021/ja0483185. PMID 15669874.
11. Bourdreux Y, Nowaczyk S, Billaud C, Mallinger A, Willis C, Murr MD, Toupet L, Lion C, Gall TL, Mioskowski C (2008). "Total synthesis of norbadione A". Journal of Organic Chemistry. 73 (1): 22–26. doi:10.1021/jo702106u. PMID 18052074.