Pacifigorgianes and tamariscene as constituents of Frullania tamarisci and Valeriana officinalis

Functional Identification of Valerena-1,10-diene Synthase, a Terpene Synthase Catalyzing a Unique Chemical Cascade in the Biosynthesis of Biologically Active Sesquiterpenes in Valeriana officinalis

“…Altogether, the one-and two-dimensional NMR data elucidated the structure of 2 as being valerena-1,10-diene. This assignment was further verified by comparison to published spectral data of valerena-1,10-diene from Paul et al (11). Additionally, the oneand two-dimensional NMR data obtained for compound 2 (valerena-1,10-diene) isolated from V. officinalis root tissue, the VoTPS1 yeast-produced compound, and that prepared synthetically by Kitayama et al (31) were identical, as were the GC 1) and valerena-1,10-diene (2).…”

“…The cultures A, multistep pathways are depicted, the first step catalyzed by a sesquiterpene synthase (TPS) cyclizing FPP to either germacrene C (1) or valerena-1,10-diene (2) followed by internal ring formation and hydroxylation/reduction (valeranone) or successive hydroxylation/oxidation at one of the terminal methyls of the isobutenyl side chain (valerenic acid). B, tamariscene (5), tamarisol (6), and pacifigorgiol (7) appear to share a valerenadiene-like scaffold in common with valerenic acid and hence may share a similar biosynthetic origin as suggested by Paul et al (11).…”

“…1). However, valerenadiene has been of particular interest to others studying related biologically active sesquiterpene compounds like tamariscol (10), tamariscene (11), and pacifigorgiol (12) (Fig. 1) because the biogenic origin of the isobutenyl substituent group common to these molecules has remained enigmatic.…”

Concise Synthesis of Valerena-4,7(11)-diene, a Highly Active Sedative, from Valerenic Acid

“…3) Characteristic peaks of one olefin and two allylic protons at the C2 and C6 positions were clearly observed. The first concise synthesis of 1 was therefore achieved in three steps from valerenic acid in a 63% total yield to provide further material for biological testing.…”

“…1, has been isolated in a small quantity from the roots of Nardostachys chinensis 1,2) and Valeriana officinalis L., 3,4) and is a bicyclic sesquiterpene that has recently been shown to dose-dependently reduce the locomotor activity of mice with a particularly profound effect, the strongest sedative activity being observed at a dose of 0.06%. 1) The unique aspect for the pharmacological activity of this compound is that it can be administered via inhalation; the compound is naturally volatile at room temperature and bears a pleasant smell.…”