A Structural Investigation of the N--B Interaction in an o-(N,N-Dialkylaminomethyl)arylboronate System.
o-(Pyrrolidinylmethyl)phenylboronic acid (4) and its complexes with bifunctional substrates such as catechol, α-hydroxyisobutyric acid, and hydrobenzoin have been studied in detail by X-ray crystallography, B NMR, and computational analysis. The N–B interactions in analogous boronic acids and esters...
| Publicado en: | Journal of the American Chemical Society Vol. 128; no. 4; pp. 1222 - 1233 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
2/1/2006
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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=20241749&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 20241749 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: 2/1/2006 vid: 128 iid: 4 pid: 997 pub: American Chemical Society artinfo: ui: 20241749 10.1021/ja055817c ppf: 1222 ppct: 11 formats: tig: atl: A Structural Investigation of the N--B Interaction in an o-(N,N-Dialkylaminomethyl)arylboronate System. aug: au: Lei Zhu Shabbir, Shagufta H. Gray, Mark Lynch, Vincent M. Sorey, Steven Anslyn, Eric V. affil: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712. su: Catechol X-ray crystallography Organic compounds Chlorohydrocarbons Trihalomethanes Structural optimization sug: subj: Catechol X-ray crystallography Organic compounds Chlorohydrocarbons Trihalomethanes Structural optimization ab: o-(Pyrrolidinylmethyl)phenylboronic acid (4) and its complexes with bifunctional substrates such as catechol, α-hydroxyisobutyric acid, and hydrobenzoin have been studied in detail by X-ray crystallography, B NMR, and computational analysis. The N–B interactions in analogous boronic acids and esters have been extensively cited in molecular recognition and chemosensing literature. The focal point of this study was to determine the factors that are pertinent to the formation of an intramolecular N–B dative bond. Our structural study predicts that the formation of an N–B dative bond, and/or solvent insertion to afford a tetrahedral boronate anion, depends on the solvent and the complexing substrate present. Specifically, from B NMR studies, complexation of 4 with electron-withdrawing and/or vicinally bifunctionalized substrates promotes both the formation of N–B dative bonds and the solvation of sp² boron to a tetrahedral sp³ boronate. In the solid state, the presence of an N–B dative bond in the complex of 4 and catechol (7) depends on the solvent from which it crystallizes. From chloroform, an N–B bond was observed, whereas from methanol, a methoxylated boronate was formed, where the methoxy group is hydrogen-bonded with the neighboring tertiary ammonium ion. The structural optimization of compounds 4 and 7 using density functional theory in a simulated water continuum also predicts that complexation of 4 and catechol promotes either the formation of an N–B bond or solvolysis if 1 equiv of water is present. The conclusion from this study will help in the design of future chemosensing technologies based on o-(N,N-dialkylaminomethyl)-arylboronate scaffolds that are targeting physiologically important substances such as saccharides, α-hydroxycarboxylates, and catecholamines. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2006 holdings: @attributes: islocal: N |
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