Cycloartane glycosides from Sutherlandia frutescens

Four new cycloartane glycosides, sutherlandiosides A-D (1-4), were isolated from the South African folk medicine Sutherlandia frutescens and their structures established by spectroscopic methods and X-ray crystallography as 1S,3R,24S,25-tetrahydroxy-7S,10S-epoxy-9,10-seco-9,19-cyclolanost-9(11)-ene 25-O-β-D-glucopyranoside (1), 3R,7S,24S,25-tetrahydroxycycloartan-1-one 25-O-β-D-glucopyranoside (2), 3R,24S,25-trihydroxycycloartane-1,11-dione 25-O-β-D- glucopyranoside (3), and 7S,24S,25-trihydroxycycloart-2-en-1-one 25-O-β-D-glucoyranoside (4). Compound 1 represents the first secocycloartane skeleton possessing a 7,10-oxygen bridge. Compounds 2-4 are also the first examples of naturally occurring cycloartanes with a C-1 ketone functionality. Biosynthetic considerations and chemical evidence suggest that the presence of the C-1 ketone in 2 may facilitate the ring opening of the strained cyclopropane system. © 2008 American Chemical Society and American Society of Pharmacognosy.