BIOLOGICALLY ACTIVE GLYCOSIDES FROM ASTEROIDEA. IV. STEROID OLIGOGLYCOSIDES FROM THE STARFISH ASTROPECTEN LATESPINOSUS MEISSNER

Three aglycones, 3β,6α,20ξ-trihydroxy-5α-cholest-9(11)-en-23-one (1), 3β,6α-dihydroxy-5α-cholesta-9(11),20(22)-dien-23-one (2), and 3β,6α-dihydroxy-5α-pregn-9(11)-en-20-one (3), were isolated in form of the diacetates (1′, 2′, and 3′) from the enzymatic hydrolysate of an oligoglycoside mixture prepared from the whole bodies of Astropecten latespinosus Meissner. Two oligoglycosides were newly isolated from solvolysis products of the same glycoside mixture. The structures were elucidated by chemical and spectroscopic evidence to be 3β,6α,20ξ-trihydroxy-23-oxo-5α-cholest-9(11)-en-6α-yl O-β-D-fucopyranosyl-(13)-O-β-D-fucopyranosyl-(12)-O-β-D-galactopyranosyl-(14)-O-[β-D-quinovopyranosyl-(12)]-O-β-D-xylopyranosyl-(13)-O-β-D-quinovopyranoside (4) and 3β,6α,20ξ-trihydroxy-23-oxo-5α-cholest-9(11)-en-6α-yl O-β-D-fucopyranosyl-(12)-O-β-D-glucopyranosyl-(14)-O-[β-D-quinovopyranosyl-(12)]-O-β-D-xylopyranosyl-(13)-O-β-D-quinovopyranoside (5). Biologisch Aktive Glycoside aus Asteroidea, IV Steroid-Oligoglycoside aus dem Seestern Astropecten latespinosus Meissner Drei Aglyca, 3β,6α,20ξ-Trihydroxy-5α-cholest-9(11)-en-23-on (1), 3β,6α-Dihydroxy-5α-cholesta-9(11),20(22)-dien-23-on (2) und 3β,6α-Dihydroxy-5α-pregn-9(11)-en-20-on (3) wurden als Acetate (1′, 2′ und 3′) aus dem enzymatischen Hydrolysat des Oligoglycosidgemisches isoliert, das aus den ganzen Seesternen Astropecten latespinosus Meissner dargestellt wurde. Zwei neue Oligoglycoside liesen sich aus dem Solvolyseprodukt des gleichen Oligoglycosidgemisches isolieren. Auf Grund chemischer und spektroskopischer Beweise wurden die Strukturen als (3β,6α,20ξ-Trihydroxy-23-oxo-5α-cholest-9(11)-en-6α-yl)-O-β-D-fucopyranosyl-(13)-O-β-D-fucopyranosyl-(12)-O-β-D-galactopyranosyl-(14)-O-[β-D-chinovopyranosyl-(12)]-O-β-D-xylopyranosyl-(13)-O-β-D-chinovopyranosid (4) und (3β,6α,20ξ-Trihydroxy-23-oxo-5α-cholest-9(11)-en-6α-yl)-O-β-D-fucopyranosyl-(12)-O-β-D-glucopyranosyl-(14)-O-[β-D-chinovopyranosyl-(12)]-O-β-D-xylopyranosyl-(13)-O-β-D-chinovopyranosid (5) ermittelt