Elusive Metal-Free Primary Amination of Arylboronic Acids: Synthetic Studies and Mechanism by Density Functional Theory.
Herein, we disclose the first metal-free synthesis of primary aromatic amines from arylboronic acids, a reaction that has eluded synthetic chemists for decades. This remarkable transformation affords structurally diverse primary arylamines in good chemical yields, including a variety of halogenated...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 44; pp. 18253 - 18257 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
11/7/2012
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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=83713765&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 83713765 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: 11/7/2012 vid: 134 iid: 44 pid: 997 pub: American Chemical Society artinfo: ui: 83713765 10.1021/ja309637r ppf: 18253 ppct: 4 formats: tig: atl: Elusive Metal-Free Primary Amination of Arylboronic Acids: Synthetic Studies and Mechanism by Density Functional Theory. aug: au: Chen Zhu Gongqiang Li Ess, Daniel H. Falck, John R. Kürti, László affil: Division of Chemistry, Department of Biochemistry, University of Texas Southwestern Medical Center, Dallas, Texas 75390, United States Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, United States su: Amination Boronic acids Density functionals Aromatic amines Organic compounds sug: subj: Amination Boronic acids Density functionals Aromatic amines Organic compounds ab: Herein, we disclose the first metal-free synthesis of primary aromatic amines from arylboronic acids, a reaction that has eluded synthetic chemists for decades. This remarkable transformation affords structurally diverse primary arylamines in good chemical yields, including a variety of halogenated primary anilines that often cannot be prepared via transition-metal-catalyzed amination. The reaction is operationally simple, requires only a slight excess of aminating agent, proceeds under neutral or basic conditions, and, importantly, can be scaled up to provide multigram quantities of primary anilines. Density functional calculations reveal that the most likely mechanism involves a facile 1,2-aryl migration and that the presence of an ortho nitro group in the aminating agent plays a critical role in lowering the free energy barrier of the 1,2-aryl migration step. 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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