Mechanism and Stereoselectivity of a Dual Amino-Catalyzed Robinson Annulation: Rare Duumvirate Stereocontrol.
Computational study of the mechanisms and stereoselectivities of a dual amino-catalyzed synthesis of cyclohexenones containing all-carbon α-quaternary and ∂-tertiary stereocenters is reported. Extensive conformational search with density functional theory optimizations, the high-accuracy SCS-MP2/cc-...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 33; pp. 13624 - 13632 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
8/22/2012
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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=79469116&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 79469116 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: 8/22/2012 vid: 134 iid: 33 pid: 997 pub: American Chemical Society artinfo: ui: 79469116 10.1021/ja3018219 ppf: 13624 ppct: 8 formats: tig: atl: Mechanism and Stereoselectivity of a Dual Amino-Catalyzed Robinson Annulation: Rare Duumvirate Stereocontrol. aug: au: Pierce, Matthew D. Johnston, Ryne C. Mahapatra, Subham Hua Yang Carter, Rich G. Cheong, Paul Ha-Yeon affil: Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97331, United States su: Cyclohexenones Density functionals Solvation Amines Aldehydes sug: subj: Cyclohexenones Density functionals Solvation Amines Aldehydes ab: Computational study of the mechanisms and stereoselectivities of a dual amino-catalyzed synthesis of cyclohexenones containing all-carbon α-quaternary and ∂-tertiary stereocenters is reported. Extensive conformational search with density functional theory optimizations, the high-accuracy SCS-MP2/cc-pV∞Z energies, and PCM solvation correction were used to characterize ail intermediates and transition states. Six mechanisms were considered, all consistent with available experiments. The reaction proceeds via sequential Michael and Mannich conjugate additions whereby the primary amine activates the aldehyde and the catalyst activates the pentenone. We have discovered a rare duumvirate stereocontrol: the Michael reaction sets the enantioselectivity, but both the Michael and the Mannich reactions control the diastereoselectivity. 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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