Effect of acyl donor chain length and substitutions pattern on the enzymatic acylation of flavonoids.
Rutin and esculin were enzymatically acylated with different aliphatic acids as acyl donors (fatty acids, dicarboxylic acids and omega-substituted fatty acids) by an immobilized lipase from Candida antarctica. The effect of the water content and the acyl donors pattern on the flavonoid initial acylation rate and conversion yield were investigated. The obtained results indicated that the water content of the medium has a strong effect on the performance of these reactions. The best conversion yields were reached when the water content was kept lower than 200 ppm. At low water content of the medium, these syntheses are influenced by carbon chain length and substitution pattern of the acyl donors. Higher conversion yields of esculin and rutin (>70%) were obtained with aliphatic acids having high carbon chain length (>12). Moreover, it has been found that the amine and thiol groups on omega-substituted fatty acid chain were unfavourable to these reactions. The 1H NMR and 13C NMR analyses of some synthesized esters (esculin and rutin palmitate) show that only monoesters were produced and that the esterification takes place on the primary OH of glucose moiety of the esculin and on the secondary 4"'-OH of the rhamnose residue of rutin.
Ardhaoui
M
M
Laboratoire Bioprocédés Agroalimentaire, ENSAIA-INPL 2, Av de la Forêt de Haye, 54500 Vandoeuvre, France.
Falcimaigne
A
A
Ognier
S
S
Engasser
J M
JM
Moussou
P
P
Pauly
G
G
Ghoul
M
M
D000215:Acylation; D002175:Candida / Q000201:enzymology; D002247:Carbon Isotopes; D002384:Catalysis; D003998:Dicarboxylic Acids / Q000737:chemistry / Q000378:metabolism; D004929:Esculin / Q000378:metabolism; D004951:Esterification; D004952:Esters / Q000138:chemical synthesis; D005227:Fatty Acids / Q000737:chemistry / Q000378:metabolism; D005240:Feasibility Studies; D005419:Flavonoids / Q000737:chemistry* / Q000378:metabolism*; D057927:Hydrophobic and Hydrophilic Interactions; D007700:Kinetics; D008049:Lipase / Q000737:chemistry / Q000378:metabolism; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D011522:Protons; D012431:Rutin / Q000096:biosynthesis; D013379:Substrate Specificity; D014867:Water / Q000737:chemistry
D002247:Carbon Isotopes; D003998:Dicarboxylic Acids; D004952:Esters; D005227:Fatty Acids; D005419:Flavonoids; D011522:Protons; D014867:Water; D004929:Esculin; D012431:Rutin; D008049:Lipase