Non-Enzymatic Oxidation of a Pentagalloylglucose Analogue into Members of the Ellagitannin Family

Abstract

The occurrence of more than 1000 structurally diverse ellagitannins has been hypothesized to begin with the oxidation of penta-O-galloyl-β-d-glucose (β-PGG) for the coupling of the galloyl groups. However, the non-enzymatic behavior of β-PGG in the oxidation is unknown. Disclosed herein is which galloyl groups tended to couple and which axial chirality was predominant in the derived hexahydroxydiphenoyl groups when an analogue of β-PGG was subjected to oxidation. The galloyl groups coupled in the following order: at the 4,6-, 1,6-, 1,2-, 2,3-, and 3,6-positions with respective S-, S-, R-, S-, and R-axial chirality. Among them, the most preferred 4,6-coupling reflected the what was observed for natural ellagitannins. A new finding was that the second best coupling occured at the 1,6-positions. With the detection of a 3,6-coupled product, this work demonstrated that even ellagitannin skeletons with an axial-rich glucose core may be generated non-enzymatically.

Keywords: C−C coupling; ellagitannins; natural products; oxidation; polyphenols.