A Theoretical Investigation on the Mechanism and Stereochemical Course of the Addition of (E)-2-Butenyltrimethylsilane to Acetaldehyde by Electrophilic and Nucleophilic Activation.
The diastereoselectivity of the addition of (E)-2-butenyltrimethylsilane to acetaldehyde under electrophilic (BF, HO) and nucleophilic (F-) activation is investigated using density functional theory (M06-2X). The interaction-distortion/activation-strain model of reactivity is used to rationalize the...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 12; pp. 4743 - 4757 |
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| Autores principales: | , |
| Formato: | Artículo |
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American Chemical Society
3/27/2013
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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=87107901&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 87107901 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: 3/27/2013 vid: 135 iid: 12 pid: 997 pub: American Chemical Society artinfo: ui: 87107901 10.1021/ja311889v ppf: 4743 ppct: 14 formats: tig: atl: A Theoretical Investigation on the Mechanism and Stereochemical Course of the Addition of (E)-2-Butenyltrimethylsilane to Acetaldehyde by Electrophilic and Nucleophilic Activation. aug: au: Wolf, Larry M. Denmark, Scott E. affil: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, United States su: Density functionals Acetaldehyde Electrophilic substitution reactions Electrophilic addition reactions Nucleophilic reactions Nucleophilic addition (Chemistry) sug: subj: Density functionals Acetaldehyde Electrophilic substitution reactions Electrophilic addition reactions Nucleophilic reactions Nucleophilic addition (Chemistry) ab: The diastereoselectivity of the addition of (E)-2-butenyltrimethylsilane to acetaldehyde under electrophilic (BF, HO) and nucleophilic (F-) activation is investigated using density functional theory (M06-2X). The interaction-distortion/activation-strain model of reactivity is used to rationalize the origin of the selectivity. Consistent with experimental model systems, the synclinal transition states are determined to be preferred over the antiperiplanar transition states in the electrophilic-activated manifolds and vice versa for the fluoride-activated manifold. The selectivity for the syn diastereomer in the electrophilic activation manifolds is accounted for by increased electrostatic and orbital interactions for a synclinal transition state (syn-T3) at the expense of increased steric interactions relative to antiperiplanar transition states. The enhanced orbital interactions for the synclinal (syn-T3) versus antiperiplanar transition states can be attributed to increased π→π* interactions. The selectivity for the anti diastereomer in the nucleophilic manifold is explained by the lesser electrostatic repulsion in the antiperiplanar transition states which are favored relative to the synclinal transition states. Additionally, the diastereoselectivity is partly attributed to variation in the distortion of the crotylsilane. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2013 holdings: @attributes: islocal: N |
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