Accelerating Effect of Triazolyl and Related Heteroaryl Substituents on SAr Reactions: Evidence of Hydrogen-Bond Stabilized Transition States.
The remarkable accelerating effect of 1,2,3- triazolyl substituents on SNAr reactions has been investigated through systematic experiments and density functional theory calculations. The lone pair electrons of an orfho-triazolo substituent play a key role in lowering the activation energy for nucleo...
| Publicado en: | Journal of the American Chemical Society Vol. 137; no. 38; pp. 12261 - 12269 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
9/30/2015
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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=110461164&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 110461164 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: 9/30/2015 vid: 137 iid: 38 pid: 997 pub: American Chemical Society artinfo: ui: 110461164 10.1021/jacs.5b06189 ppf: 12261 ppct: 8 formats: tig: atl: Accelerating Effect of Triazolyl and Related Heteroaryl Substituents on SAr Reactions: Evidence of Hydrogen-Bond Stabilized Transition States. aug: au: Wenyuan Qian Hao Wang Bartberger, Michael D. affil: Department of Medicinal Chemistry, Therapeutic Discovery, Amgen Inc., One Amgen Center Drive, Thousand Oaks, California 91320-1799, United States Department of Molecular Structure, Therapeutic Discovery, Amgen Inc., One Amgen Center Drive, Thousand Oaks, California 91320-1799, United States su: Aryl group Substituents (Chemistry) Hydrogen bonding Transition state theory (Chemistry) Tin alloys Density functional theory sug: subj: Aryl group Substituents (Chemistry) Hydrogen bonding Transition state theory (Chemistry) Tin alloys Density functional theory ab: The remarkable accelerating effect of 1,2,3- triazolyl substituents on SNAr reactions has been investigated through systematic experiments and density functional theory calculations. The lone pair electrons of an orfho-triazolo substituent play a key role in lowering the activation energy for nucleophilic addition via formation of a preferential hydrogen bond with the amine nucleophile at the transition state for addition. In an extension of this finding, a series of related heteroaryl groups with similar electron pair donor properties have also been found to facilitate SNAr reactions. The experimentally determined solvent effect provides further support for this rationale, which was utilized to achieve an ortho-selective substitution on a difluoroarene substrate. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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