Secondary diterpene

Stypodiol, epistypodiol and stypotriol are secondary diterpene metabolites produced by the tropical brown algae Stypopodium zonaie. These compounds display diverse biological properties, including strong toxic, narcotic, and hyperactive effects upon the reef-dwelling fish. In the laboratory of A. Abad an efficient stereoselective synthesis of stypodiol and its C14 epimer, epistypodiol, was accomplished from (S)-(+)-carvone. The key transformations in the synthesis of these epimeric compounds were an intramolecular Diels-Alder reaction, a sonochemical Barbier reaction and an acid-catalyzed quinol-tertiary alcohol cyclization. 

In 1992, Paul and Van Alstyne reported on the processes that occur after tissue disruption in different species of the calcified green seaweed Halimeda [56]. After wounding, these algae transform their major secondary metabolite, the his-enoylacetate diterpene halimedatetraacetate (48), into halimedatrial (50) and epihalimedatrial (51). The structural relationship between the educt and the reaction products suggests that the transformation occurs by a combination of solvolysis and hydrolysis reactions as indicated in Scheme 14 [108]. 

A recent example demonstrates that corals rely on induced biosynthesis of terpenes as a dynamic defense strategy as well. The induction of terpenoid secondary metabolites was observed in the sea whip Pseudopterogorgia elisabethae [162]. Levels of pseudopterosins 89-92, a group of diterpene glycosides with anti-inflammatory and analgesic properties (Scheme 23) [163-165], are increased in response predation by the mollusk Cyphoma gibbosum. First bioassays indicate that these natural products are involved in the chemical defense. 

Low susceptibility to reef fishes in Florida and produces secondary metabolites (Paul and Hay 1986). Crude extract from Guam specimens inhibits herbivory by reef fishes (Paul 1987) crude extract and a mixture of two diterpenes inhibits herbivory by the gastropod Astraea latispina (Pereira et al. 2002)... 

Schmitt TM, Lindquist N, Hay ME (1998) Seaweed secondary metabolites as antifoulants effects of Dictyota spp. diterpenes on survivorship, settlement, and development of invertebrate larvae. Chemoecology 8 125-131... 

Solldago is a mostly North American genus of about 125 species. It belongs to the Asteraceae (Compositae), a family with a very distinctive chemistry (57, 58). The genus itself contains several different classes of secondary compounds including a number of diterpenes (59). During the 1960 s and 1970 s Anthonsen in Finland, and McCrindle and his coworkers in Canada, isolated about twenty-five different compounds from the roots of Solidago species, mainly clerodanes and labdanes. But in the last five years attention has turned to the aerial parts of the plant and compounds of several other classes of diterpenes, abietanes and kauranes, have been isolated (60-79) (Table II). 

Overall, however, the immensity of temperate land corresponds to a most various secondary metabolic production, different from that of tropical land. The most renowned alkaloids belong to the morphine class (Chart 6.2.A1), and, in combination with isoprenoids, to the ergot and triterpene classes (Chart 6.2. A2). Prominent in the peptides are the cyclosporins (the first of which was isolated from a fiingus collected in Norway), streptogramins, and P-lactams (Chart 6.2.P). The isoprenoids are represented by pyrethrin monoterpenes, cedrane sesquiterpenes, ginkgolide and taxane diterpenes, ophiobolane sesterterpenes, and arborane and amyrin-like triterpenes (Chart 6.2.1). In the polyketides, epothilones, recently discovered from Myxobacteria, and the long known rapamycin, are two prominent classes of macrolides (Chart 6.2.FA/PO/C). 

Phytochemical studies of these species led to the isolation and structural characterization, by NMR and MS analysis, of many secondary metabolites, mainly flavonoids, and expecially flavonol glycosides, clerodane diterpenes, and triterpenes having the lupane, ursane, and oleanane skeletons. Particularly flavonoids and their glycosides have a chemotaxonomic interest in the genus and in general in the Chrysobalanaceae family. 

In the course of our phytochemical work we studied seven Licania species all belonging to Venezuelan flora, collected in Puerto Ayacucho, Estado Amazonas and in the Parque Nacional Henry Pittieri, Maracay, Estado Aragua. A number of new and known secondary metabolites, mainly flavonoids, especially flavonol glycosides, sterols, and triterpenes having the lupane, ursane, and oleanane skeleton were isolated and characterized. The last part of this chapter deals also with the isolation of clerodane diterpenes from the methanol extract of L. intrapetiolaris by Oberlies et al., 2001 [4]. All the Licania species investigated up to now are reported in Table 1. 

Biologically active secondary metabolites from fungi. 12. Oidiolactones A-F, labdane diterpene derivatives isolated from Oidiodendron truncata. John, M. Krohn, K. Florke, U. Aust, H-J. Draeger, S. Schulz, B. J. Nat. Prod. 1999, 62, 1218-1221. 

The typical secondary metabolites of soft corals are diterpenoids, although some species also produce sesquiterpenoids. The sesquiterpene portion of furoquinol (Structure 2.102) is labeled by [2-3H]mevalonolactone in Sinularia capillosa,m while Heteroxenia sp. converts acetate and meva-lonate into cubebol (Structure 2.103) and clavukerin A (Structure 2.104).188 In contrast, acetate is used for cetyl palmitate synthesis in Alcyonium molle, but not for de novo diterpene biosynthesis.188... 

---