Computational Exploration of Concerted and Zwitterionic Mechanisms of Diels-Alder Reactions between 1,2,3-Triazines and Enamines and Acceleration by Hydrogen-Bonding Solvents.
The mechanisms of Diels−Alder reactions between 1,2,3- triazines and enamines have been explored with density functional theory computations. The focus of this work is on the origins of the different reactivities and mechanisms induced by substituents and by hexafluoroisopropanol (HFIP) solvent. T...
| Publicado en: | Journal of the American Chemical Society Vol. 139; no. 50; pp. 18213 - 18222 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
12/20/2017
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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=127093237&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 127093237 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: 12/20/2017 vid: 139 iid: 50 pid: 997 pub: American Chemical Society artinfo: ui: 127093237 10.1021/jacs.7b08325 ppf: 18213 ppct: 9 formats: tig: atl: Computational Exploration of Concerted and Zwitterionic Mechanisms of Diels-Alder Reactions between 1,2,3-Triazines and Enamines and Acceleration by Hydrogen-Bonding Solvents. aug: au: Yun-Fang Yang Peiyuan Yu Houk, K. N. affil: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States su: Zwitterions Diels-Alder reaction Triazines Hydrogen bonding interactions Enamines Density functional theory sug: subj: Zwitterions Diels-Alder reaction Triazines Hydrogen bonding interactions Enamines Density functional theory ab: The mechanisms of Diels−Alder reactions between 1,2,3- triazines and enamines have been explored with density functional theory computations. The focus of this work is on the origins of the different reactivities and mechanisms induced by substituents and by hexafluoroisopropanol (HFIP) solvent. These inverse electron-demand Diels−Alder reactions of triazines have wide applications in bioorthogonal chemistry and natural product synthesis. Both concerted and stepwise cycloadditions are predicted, depending on the nature of substituents and solvents. The nature of zwitterionic intermediates and the mechanism by which HFIP accelerates cycloadditions with enamines are characterized. Our results show the delicate nature of the concerted versus stepwise mechanism of inverse electron-demand Diels−Alder reactions of 1,2,3-triazines, and that these mechanisms can be altered by electron-withdrawing substituents and hydrogen-bonding solvents. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
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