A Dimer of Puupehenone

Abstract

SummaryThe structure of a colorless dimer (4a) of puupehenone (l), which was isolated from Pacific marine sponges, has been elucidated from spectral data.Marine sponges are a rich source of secondary metabolites, particularly terpenoids [ 11. Occasionally, compounds of mixed biosynthesis have been encountered, among them the puupehenones 1-3, which are constructed of sesquiterpene and benzene moieties [2]. The yellow encrusting sponge, identified as Heteronenza sp. (family Spongiidue, order Dictyoceratidu, class Demospongiae), from which puupehenone (1) was originally isolated, was first collected by us off the Hawaiian islands of Lanai and Oahu. The halopuupehenones 2 and 3 were minor constituents in a Heteronemu sample from Enewetak in the Marshall islands. In all collections we encountered several dimeric compounds, some of them highly colored. A colorless dimer, bispuupehenone (4a). was subsequently also isolated from a Tahitian sponge, Hjrtios (= Inodes) eubumma (family Thorectidae, order Dictyoceratida), and is the subject of this report.H. eubumma was preserved in EtOH and then further extracted with the same solvent. The aqueous residue was partitioned with cyclohexane. Chromatography of the organic residue on Sephadex, then silica gel, yielded puupehenone (1) and bispuupehenone (4a), m.p. 234-240". A composition of C42H5406 was ascertained by mass spectrometry. The fragmentation pattern, including abundant M + -15 (m/z 639) and M + -151 (see wiggly line in 4) ions, were reminiscent of the puupehenone spectrum [2]. The presence of OH-groups was indicated by IR bands at 3560 and 3420 cm-I.The I3C-NMR spectrum displayed 2 1 signals, thus confirming that bispuupehenone (4a),is a symmetrical dimer of 1. Fifteen upfield signals parallel those of other drimane derivatives, e.g. 1, its methanol adduct 5, or 8-epichromazonarol (6) [3] I )

Pleiotropic Role of Puupehenones in Biomedical Research

“…The 1,6-Conjugated nucleophilic addition of HCN to puupehenone in the presence of water and alkaline conditions yields 15α-cyanopuupehenol and its oxidation product 15α-cyanopuupehenone [ 6 ]. Addition of oxygen nucleophiles such as acetoxy and methoxy ions to puupehenone (obtaining 15α-acetoxypuupehenol diacetate and 15α-methoxypuupehenol) has been also reported [ 4 , 10 ]. A large number of puupehenone-derived/related compounds, either naturally occurring or of synthetic origin, has been reported in the literature [ 11 ].…”

Drimane-Related Merosesquiterpenoids, a Promising Library of Metabolites for Drug Development

“…Bispuupehenone (514), the first dimeric puupehenone, was reported from the marine sponge Hyrtios eubamma [333]. Dipuupehetriol (515) and dipuupehedione (516) were found in an unidentified marine sponge and Hyrtios sp., respectively [233,334].…”

Meroterpenes from Marine Invertebrates: Structures, Occurrence, and Ecological Implications

“…Puupehenone ( 185 ) possessing a drimane skeleton differs from typical natural sesquiterpene quinones by having a quinone–methide system. First isolated by Scheuer and co-workers from the sponge tentatively identified as Chondrosia chucalla [129], 185 has so far been isolated from different sponges, mainly of orders Verongida and Dictyoceratida, together with many other puupehenone-derived congeners ( 186 – 192 ) engendered by the presence of the highly electrophilic quinone–methide system and oxygen functionalities [129,130,131,132,133,134,135,136,137] (Figure 11). The puupehenones display a wide range of biological properties as angiogenesis inhibitors [138], antitumor [130,131], antifungal [48,129], antiviral [48], antimalarial [130], antituberculosis [139], immunomodulatory [138,140], and antioxidant agents [141].…”

“…and Hyrtios sp. [131,137,141]. The unsymmetrical structure of diplopuupehenone comprises puupehenone and puupehenol segments.…”