The Need for Enzymatic Steering in Abietic Acid Biosynthesis: Gas-Phase Chemical Dynamics Simulations of Carbocation Rearrangements on a Bifurcating Potential Energy Surface.
Abietic acid, a constituent of pine resin, is naturally derived from abietadiene - a process that requires four enzymes: one (abietadiene synthase) for conversion of the acyclic, achiral geranylgeranyl diphosphate to the polycydic, chiral abietadiene (a complex process involving the copalyl diphosph...
| Publicado en: | Journal of the American Chemical Society Vol. 133; no. 21; pp. 8335 - 8344 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
6/1/2011
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=61341141&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 61341141 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 6/1/2011 vid: 133 iid: 21 pid: 997 pub: American Chemical Society artinfo: ui: 61341141 10.1021/ja201730y ppf: 8335 ppct: 9 formats: tig: atl: The Need for Enzymatic Steering in Abietic Acid Biosynthesis: Gas-Phase Chemical Dynamics Simulations of Carbocation Rearrangements on a Bifurcating Potential Energy Surface. aug: au: Siebert, Matthew R. Jiaxu Zhang Addepalli, Srirangam V. Tantillo, Dean J. Hase, William L. affil: Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409, United States High Performance Computing Center, Texas Tech University, Lubbock, Texas 79409, United States Department of Chemistry, University of California-Davis, Davis, California 95616, United States su: Enzymatic analysis Abietic acid Biosynthesis Carbocations Carboxylic acids Potential energy surfaces Enzymes sug: subj: Enzymatic analysis Abietic acid Biosynthesis Carbocations Carboxylic acids Potential energy surfaces Enzymes ab: Abietic acid, a constituent of pine resin, is naturally derived from abietadiene - a process that requires four enzymes: one (abietadiene synthase) for conversion of the acyclic, achiral geranylgeranyl diphosphate to the polycydic, chiral abietadiene (a complex process involving the copalyl diphosphate intermediate) and then three to oxidize a single methyl group of abietadiene to the corresponding carboxylic acid. In previous work (Nature Chem. 2009, 1, 384), electronic structure calculations on carbocation rearrangements leading to abietadienyl cation revealed an interesting potential enerysurface with a bifurcating reaction pathway (two transition-state structures connected directly with no intervening minimum), which links two products - one natural and one not yet isolated from Nature. Herein we describe direct dynamics simulations of the key step in the formation of abietadiene (in the gas phase and in the absence of the enzyme). The simulations reveal that abietadiene synthase must intervene in order to produce abietadiene selectively, in essence steering this reaction to avoid the generation of byproducts with different molecular architectures. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2011 holdings: @attributes: islocal: N |
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