Transition-Metal-Free Direct Arylation: Synthesis of Halogenated 2-Amino-2'-hydroxy-1,1'-biaryls and Mechanism by DFT Calculations.
A transition-metal-free, regioselective direct aryl–aryl bond-forming process for the synthesis of halogenated 2-amino-2'-hydroxy-1,1'-biaryls that are currently either inaccessible or challenging to prepare using conventional methods is disclosed. The addition of ArMgX to an o-halonitrobenzene at l...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 19; pp. 7086 - 7090 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
5/15/2013
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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=87833382&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 87833382 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: 5/15/2013 vid: 135 iid: 19 pid: 997 pub: American Chemical Society artinfo: ui: 87833382 10.1021/ja400897u ppf: 7086 ppct: 4 formats: tig: atl: Transition-Metal-Free Direct Arylation: Synthesis of Halogenated 2-Amino-2'-hydroxy-1,1'-biaryls and Mechanism by DFT Calculations. aug: au: Hongyin Gao Ess, Daniel H. Yousufuddin, Muhammed Kürti, László affil: Division of Chemistry, Department of Biochemistry, UT Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, Texas 75390, United States Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, United States Center for Nanostructured Materials, The University of Texas at Arlington, Arlington, Texas 76019, United States su: Aromatic compound synthesis Arylation Density functional theory Transition metal catalysts Regioselectivity (Chemistry) Nitrobenzene Bond formation mechanism sug: subj: Aromatic compound synthesis Arylation Density functional theory Transition metal catalysts Regioselectivity (Chemistry) Nitrobenzene Bond formation mechanism ab: A transition-metal-free, regioselective direct aryl–aryl bond-forming process for the synthesis of halogenated 2-amino-2'-hydroxy-1,1'-biaryls that are currently either inaccessible or challenging to prepare using conventional methods is disclosed. The addition of ArMgX to an o-halonitrobenzene at low temperature generates a transient N,O-biarylhydroxylamine that rapidly undergoes either [3,3]- or [5,5]-sigmatropic rearrangement in one-pot to form a 2-amino-2'-hydroxy-1,1'-biaryl or 1-amino-1'-hydroxy-4,4'-biaryl, respectively. The periselectivity is controlled by the choice of solvent and temperature. This direct arylation process is also readily scalable (1–10 mmol). DFT calculations suggest that from the N,O-biarylhydroxylamine intermediate there is a low-energy stepwise pathway that involves initial Mg-mediated N–O bond cleavage followed by pathway branching toward either [3,3]- or [5,5]-rearrangement products via C–C bond formation and rearomatization. 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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