Causation in a Cascade: The Origins of Selectivities in Intramolecular Nitrone Cycloadditions.
The factors controlling chemo-, regio-, and stereoselectivity in a cascade of reactions starting from a bis(cyanoalkenyl)oxime and proceeding via nitrone cyclo- additions have been unraveled through a series of density functional theory calculations with several different functionals. Both kinetic a...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 29; pp. 12010 - 12016 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
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American Chemical Society
7/25/2012
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| Materias: | |
| 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=78336747&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 78336747 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: 7/25/2012 vid: 134 iid: 29 pid: 997 pub: American Chemical Society artinfo: ui: 78336747 10.1021/ja300002k ppf: 12010 ppct: 6 formats: tig: atl: Causation in a Cascade: The Origins of Selectivities in Intramolecular Nitrone Cycloadditions. aug: au: Krenske, Elizabeth H. Agopcan, Sesil Aviyente, Viktorya Houk, K. N. Johnson, Brian A. Holmes, Andrew B. affil: School of Chemistry, University of Melbourne, VIC 3010, Australia Australian Research Council Centre of Excellence for Free Radical Chemistry and Biotechnology Chemistry Department, Bogazici University, 34342 Bebek, Istanbul, Turkey Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States CSIRO Materials Science and Engineering, Bag 10, Clayton South, VIC 3169, Australia su: Nitrones Ring formation (Chemistry) Regioselectivity (Chemistry) Density functionals Chemical models Thermodynamics sug: subj: Nitrones Ring formation (Chemistry) Regioselectivity (Chemistry) Density functionals Chemical models Thermodynamics ab: The factors controlling chemo-, regio-, and stereoselectivity in a cascade of reactions starting from a bis(cyanoalkenyl)oxime and proceeding via nitrone cyclo- additions have been unraveled through a series of density functional theory calculations with several different functionals. Both kinetic and thermodynamic control of the reaction cascade are important, depending upon the conditions. Kinetic control was analyzed by the distortion/interaction model and found to be dictated by differences in distortions of the cycloaddends in the transition states. A new mechanism competing with that originally proposed in the application of these reactions to the histrionicotoxin synthesis was discovered in these studies. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2012 holdings: @attributes: islocal: N |
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