Degradation of the plant flavonoid phellamurin by Aspergillus niger

We have previously described the structure of phellamurin, a plant flavonoid, as 3,4',5,7-tetrahydroxy-8-isoprenylflavanone-7-O-glucoside (17). Degradation of phellamurin by Aspergillus niger using modified Czapek-Dox medium as well as phellamurin or one of its degradation products as a sole carbon source, is reported here. Eleven compounds are identified from phellamurin degradation products. A. niger apparently decomposes phellamurin by first removing glucose with beta-glucosidase; neophellamuretin is the first degradation product. Fission of the heterocyclic ring of (5''-hydroxyisopropyl-4'',5''-dihydrofurano)[2'',3''-h]3,4',5-trihydroxyflavanone, which is obtained from neophellamuretin through a few alterations of the side chain, is followed by cleavage of a C--C bond between C=O and carbon at alpha-position and conversion of (5''-hydroxyisopropyl-4'',5''-dihydrofurano)[2'',3''-d]-2',4,6',alpha-tetrahydroxychalcone to rho-hydroxymandelic acid (B-ring) and 2,4,6-trihydroxy-5-carboxyphenylacetic acid (A-ring). It is suggested that rho-hydroxymandelic acid is oxidized to rho-hydroxybenzoic acid. 2,4,6-Trihydroxy-5-carboxyphenylacetic acid is metabolized to phloroglucinol carboxylic acid, which subsequently is decarboxylated to phloroglucinol. These results provided new information on the isoprene unit metabolism of the side chain of phellamurin and firmly established the degradation pathway of phellamurin by A. niger.