Studies on the biosynthesis of pentalenolactone. III. Isolation of a biosynthetic intermediate hydrocarbon, pentalenene.

New triquinane and gymnomitrane sesquiterpenes from fermentation of the basidiomycete Antrodiella albocinnamomea

“…The first example of triquinane-type sesquiterpene was hirsutane, which was isolated from a higher fungus Stereum hirsutum in 1947 [18]. Up to date, a series of triquinane-type sesquiterpenes were isolated from fungi [4,5,19], plants [20], as well as Streptomyces [21,22]. Those sesquiterpenes were formed via the humulane-protoilludane biosynthetic pathway.…”

Trinuclear metal clusters in catalysis by terpenoid synthases

“…The crystal structures of two bacterial sesquiterpene cyclases have been solved, and both derive from Actinomycetales : pentalenene synthase from Streptomyces UC5319 [47] and epi-isozizaene synthase from Streptomyces coelicolor [43,48]. Pentalenene synthase catalyzes the cyclization of FPP to form the tricyclic sesquiterpene pentalenene in the first committed step in the biosynthesis of the pentalenolactone family of antibiotics [49]. Although the structure of pentalenene synthase was the first to be reported of a terpenoid cyclase and demonstrated that the terpenoid cyclase shared the FPP synthase fold first observed for avian FPP synthase [17], no structure of this bacterial terpenoid cyclase complexed with metal ions is available.…”

Nature as organic chemist

“…In the event we obtained 13 C-labeled pentalenolactone with a pattern of 13 C NMR signal enhancements and couplings that were nominally consistent with the well-known conversion of acetate to mevalonate and thence to FPP. 21 The endogenously generated 13 C-labeled FPP would then be cyclized to the parent tricyclic hydrocarbon pentalenene (8), 22 which would be converted to pentalenolactone by an unspecified series of oxidation steps. Curiously, the 13 C NMR spectrum of the resulting labeled pentalenolactone displayed an additional pair of 13 C- 13 C couplings that we could not explain at the time.…”