The first 60-O-sulfated phenylanthraquinones: isolation from Bulbine frutescens, structural elucidation, enantiomeric purity, and partial synthesis

Abstract

From the roots of Bulbine frutescens, the first sulfated phenylanthraquinones were isolated, together with their known sulfate-free analogs. Their structures were elucidated by spectroscopic and chiroptical methods, by acid hydrolysis or by partial synthesis. The new compounds have the usual stereo-orientation at the biaryl axis (i.e., with the acetyl portion above the anthraquinone plane) except for sodium ent-knipholone 60-O-sulfate (and thus, also its hydrolysis product, ent-knipholone), which exhibit an opposite axial configuration. We also describe the first stereoanalysis of natural phenylanthraquinones, some of which were found to be not enantiomerically pure, some even nearracemic. We furthermore, report on the first X-ray structure analysis of a phenylanthraquinone, viz. 40-O-demethylknipholone.