23515-88-0Relevant articles and documents
A multiproduct terpene synthase from medicago truncatula generates cadalane sesquiterpenes via two different mechanisms
Garms, Stefan,Koellner, Tobias G.,Boland, Wilhelm
supporting information; experimental part, p. 5590 - 5600 (2010/11/20)
Terpene synthases are responsible for a large diversity of terpene carbon skeletons found in nature. The multiproduct sesquiterpene synthase MtTPS5 isolated from Medicago truncatula produces 27 products from farnesyl diphosphate (1, FDP). In this paper, we report the reaction steps involved in the formation of these products using incubation experiments with deuterium-containing substrates; we determined the absolute configuration of individual products to establish the stereochemical course of the reaction cascade and the initial conformation of the cycling substrate. Additional labeling experiments conducted with deuterium oxide showed that cadalane sesquiterpenes are mainly produced via the protonation of the neutral intermediate germacrene D (5). These findings provide an alternative route to the general accepted pathway via nerolidyl diphosphate (2, NDP) en route to sesquiterpenes with a cadalane skeleton. Mutational analysis of the enzyme demonstrated that a tyrosine residue is important for the protonation process.
The role of germacrene D as a precursor in sesquiterpene biosynthesis: Investigations of acid catalyzed, photochemically and thermally induced rearrangements
Buelow, Nils,Koenig, Wilfried A
, p. 141 - 168 (2007/10/03)
Germacrene D is considered as a precursor of many sesquiterpene hydrocarbons. We have investigated the acid catalyzed as well as the photochemically and thermally induced rearrangement processes of germacrene D isolated from several Solidago species, which contain both enantiomers of germacrene D. Enantiomeric mixtures of sesquiterpenes of the cadinane, eudesmane (selinane), oppositane, axane, isodaucane, and bourbonane group as well as isogermacrene D were identified as main products and made available as reference compounds for structure investigations and stereochemical assignments of plant constituents. δ-Amorphene, one of the rearrangement products, was identified as a natural product for the first time. The absolute configuration of γ-amorphene was revised by correlation with the absolute configuration of germacrene D. The mechanisms of the rearrangement reactions are discussed. (C) 2000 Elsevier Science Ltd.
Synthesis of (+/-)-α-Cadinene
Vig, O. P.,Bari, S. S.,Sharma, M. L.,Dua, D. M.
, p. 145 - 146 (2007/10/02)
Oxirane (III), prepared from 6-methyl-4-(1'-methylethyl)-3,4,4a,7,8,8a-hexahydro-1(2H)naphthalenone by reaction with dimethyloxosulphonium methylide, when cleaved with lithium diisopropylamide affords 1-hydroxymethyl-6-methyl-4-(1'-methylethyl)-3,4,4a,7,8,8a-hexahydronaphthalene (IV).Mesylate (V) from IV on treatment with LAH yields the (+/-)-α-cadinene(I).
