Chromones Featuring a [6,6]-Spiroketal Moiety Produced by Coculture of the Endophytic Fungi Chaetomium virescens and Xylaria Grammica

Under the guidance of HPLC-DAD analysis, ten new chromones featuring a rare [6,6]-spiroketal moiety, namely chaetovirexylariones A–J (1–10), together with two known congeners (11–12), were isolated from coculture of the endophytic fungi Chaetomium virescens and Xylaria grammica, from the rhizome of the medicinal plant Smilax glabra Roxb. Their structures were elucidated via a combination of NMR and HRESIMS data, and the absolute configurations of 1–10 were determined by the chemical conversion and single-crystal X-ray diffraction (Cu Kα) experiments, as well as the comparison of the experimental and calculated electronic circular dichroism (ECD) data. Compound 6 is the first report as a racemate of this type of natural product. Compound 10 represents the first example of a [6,6]-spiroketal chromone bearing a 5-amino-3-methyl-2-pentenoic acid fragment. Compound 8 demonstrated a reduction in PTX resistance of SW620/AD300 by a factor of 45, and had the potential to be an effective P-gp inhibitor and an antitumor chemotherapy sensitizer.