512-61-8Relevant articles and documents
Mechanism-Based Post-Translational Modification and Inactivation in Terpene Synthases
Kersten, Roland D.,Diedrich, Jolene K.,Yates, John R.,Noel, Joseph P.
, p. 2501 - 2511 (2015/12/01)
Terpenes are ubiquitous natural chemicals with diverse biological functions spanning all three domains of life. In specialized metabolism, the active sites of terpene synthases (TPSs) evolve in shape and reactivity to direct the biosynthesis of a myriad of chemotypes for organismal fitness. As most terpene biosynthesis mechanistically involves highly reactive carbocationic intermediates, the protein surfaces catalyzing these cascade reactions possess reactive regions possibly prone to premature carbocation capture and potentially enzyme inactivation. Here, we show using proteomic and X-ray crystallographic analyses that cationic intermediates undergo capture by conserved active site residues leading to inhibitory self-alkylation. Moreover, the level of cation-mediated inactivation increases with mutation of the active site, upon changes in the size and structure of isoprenoid diphosphate substrates, and alongside increases in reaction temperatures. TPSs that individually synthesize multiple products are less prone to self-alkylation then TPSs possessing relatively high product specificity. In total, the results presented suggest that mechanism-based alkylation represents an overlooked mechanistic pressure during the evolution of cation-derived terpene biosynthesis.
Identification of &α-Santalenoic and endo-&β-Bergamotenoic Acids as Moth Oviposition Stimulants from Wild Tomato Leaves
Coates, Robert M.,Denissen, Jon F.,Juvik, John A.,Babka, Barbara A.
, p. 2186 - 2192 (2007/10/02)
The presence of oviposition-stimulating phytochemicals in hexane extracts of whole leaves of wild tomato (Lycopersicon hirsutum) accession LA 1777 was indicated by oviposition preference assays with gravid female Heliothis zea (Boddie) moths.Three sesquiterpenes isolated from these extracts were identified as (+)-(E)-α-santalen-12-oic acid (1a), (+)-(E)-endo-β-bergamoten-12-oic acid (2a), and (-)-(E)-endo-α-bergamoten-12-oic acid (3a).Structure assignments based primarily on 1H and 13C NMR spectral interpretations were confirmed by conversion to the parent sesquiterpene hydrocarbons and subsequent comparisons with authentic endo-β-bergamotene and/or literature data.The identity of 1a was verified by comparison of its methyl ester (1b) with a sample synthesized from (+)-α-santalol (9).Quantitative assays demonstrated that the two major sesquiterpene acids, 1a and 2a, are the principal oviposition stimulants in the tomato leaf extracts and that the activity of 2a is about twice that of 1a.
Synthesis of campherenone, epicampherenone, beta-santalene, epi-beta-santalene, alpha-santalene, ylangocamphor, copacamphor, and sativene.
Hodgson,MacSweeney,Money
, p. 2113 - 2130 (2007/10/05)
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