Biotransformation of β-Mangostin by an Endophytic Fungus of Garcinia mangostanato Furnish Xanthenes with an Unprecedented Heterocyclic Skeleton

Biotransformation of β-mangostin (1) by the endophytic fungus Xylaria feejeensisGM06 afforded hexacyclic ring-fused xanthenes with an unprecedented hexacyclic heterocylic skeleton. β-Mangostin (1) was transformed to two diastereomeric pairs of enantiomers, mangostafeejin A [(−)-2a/(+)-2b)] and mangostafeejin B [(−)-3a/(+)-3b)]. The chemical structures of the transformation products were elucidated by analysis of NMR and MS data, and the structure of mangostafeejin A [(−)-2a/(+)-2b)] was confirmed by single-crystal X-ray diffraction analysis. The absolute configurations of 3aand 3bwere established on the basis of calculated and measured ECD data using the ECD spectra of 2aand 2bas models. The fungal biotransformation described herein provides an effective method to convert an abundant achiral plant natural product scaffold into new chiral heterocyclic scaffolds representing expanded chemical diversity for biological activity screening.