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First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics
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| Zeitschriftentitel: | European Journal of Organic Chemistry |
|---|---|
| Personen und Körperschaften: | , , , , , , , , , |
| In: | European Journal of Organic Chemistry, 2019, 2019, 31-32, S. 5549-5556 |
| Format: | E-Article |
| Sprache: | Englisch |
| veröffentlicht: |
Wiley
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| Schlagwörter: |
| author_facet |
Perna, Filippo M. Falcicchio, Aurelia Salomone, Antonio Milet, Anne Rizzi, Rosanna Hamdoun, Ghanem Barozzino‐Consiglio, Gabriella Stalke, Dietmar Oulyadi, Hassan Capriati, Vito Perna, Filippo M. Falcicchio, Aurelia Salomone, Antonio Milet, Anne Rizzi, Rosanna Hamdoun, Ghanem Barozzino‐Consiglio, Gabriella Stalke, Dietmar Oulyadi, Hassan Capriati, Vito |
|---|---|
| author |
Perna, Filippo M. Falcicchio, Aurelia Salomone, Antonio Milet, Anne Rizzi, Rosanna Hamdoun, Ghanem Barozzino‐Consiglio, Gabriella Stalke, Dietmar Oulyadi, Hassan Capriati, Vito |
| spellingShingle |
Perna, Filippo M. Falcicchio, Aurelia Salomone, Antonio Milet, Anne Rizzi, Rosanna Hamdoun, Ghanem Barozzino‐Consiglio, Gabriella Stalke, Dietmar Oulyadi, Hassan Capriati, Vito European Journal of Organic Chemistry First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics Organic Chemistry Physical and Theoretical Chemistry |
| author_sort |
perna, filippo m. |
| spelling |
Perna, Filippo M. Falcicchio, Aurelia Salomone, Antonio Milet, Anne Rizzi, Rosanna Hamdoun, Ghanem Barozzino‐Consiglio, Gabriella Stalke, Dietmar Oulyadi, Hassan Capriati, Vito 1434-193X 1099-0690 Wiley Organic Chemistry Physical and Theoretical Chemistry http://dx.doi.org/10.1002/ejoc.201900949 <jats:p>Oxetanes are key synthons for asymmetric synthesis and also effective in directing <jats:italic>ortho</jats:italic>‐lithiation. This work first reports the solution and the solid‐state structure of an <jats:italic>ortho</jats:italic>‐lithiated aryloxetane (<jats:bold>1‐Li</jats:bold>) in the presence/absence of a bidentate ligand such as <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>,<jats:italic>N′</jats:italic>,<jats:italic>N′</jats:italic>‐tetramethylethylenediamine (TMEDA). Single crystal X‐ray diffraction analysis of <jats:bold>1‐Li</jats:bold> revealed a singular crystallographic structure in which the asymmetric unit comprises a core where the lithium atom is coordinated to the nitrogen atom of half a molecule of TMEDA and intramolecularly stabilised by the oxetane ring oxygen. This aggregation state is unprecedented in <jats:italic>ortho</jats:italic>‐lithiated arenes. Variable temperatures multinuclear magnetic resonance (<jats:sup>1</jats:sup>H, <jats:sup>7</jats:sup>Li, <jats:sup>13</jats:sup>C) mono‐ and two‐dimensional NMR studies and DFT computations supported the coexistence in solution of three chelated bridged dimeric aggregates, in slow equilibration at 180 K. The major isomer is an heterochiral aggregate on the basis of <jats:sup>1</jats:sup>H,<jats:sup>7</jats:sup>Li‐HOESY and <jats:sup>1</jats:sup>H,<jats:sup>1</jats:sup>H‐NOESY experiments. Conclusions were supported by the preparation of enantiomerically enriched (<jats:italic>S</jats:italic>)‐<jats:bold>1‐Li</jats:bold>. The privileged formation of homochiral aggregates from racemic mixtures may also have implications for the development of chiral resolution processes.</jats:p> First Direct Evidence of an <i>ortho</i>‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics European Journal of Organic Chemistry |
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10.1002/ejoc.201900949 |
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European Journal of Organic Chemistry |
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| title |
First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_unstemmed |
First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_full |
First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_fullStr |
First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_full_unstemmed |
First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_short |
First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_sort |
first direct evidence of an <i>ortho</i>‐lithiated aryloxetane: solid and solution structure, and dynamics |
| topic |
Organic Chemistry Physical and Theoretical Chemistry |
| url |
http://dx.doi.org/10.1002/ejoc.201900949 |
| publishDate |
2019 |
| physical |
5549-5556 |
| description |
<jats:p>Oxetanes are key synthons for asymmetric synthesis and also effective in directing <jats:italic>ortho</jats:italic>‐lithiation. This work first reports the solution and the solid‐state structure of an <jats:italic>ortho</jats:italic>‐lithiated aryloxetane (<jats:bold>1‐Li</jats:bold>) in the presence/absence of a bidentate ligand such as <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>,<jats:italic>N′</jats:italic>,<jats:italic>N′</jats:italic>‐tetramethylethylenediamine (TMEDA). Single crystal X‐ray diffraction analysis of <jats:bold>1‐Li</jats:bold> revealed a singular crystallographic structure in which the asymmetric unit comprises a core where the lithium atom is coordinated to the nitrogen atom of half a molecule of TMEDA and intramolecularly stabilised by the oxetane ring oxygen. This aggregation state is unprecedented in <jats:italic>ortho</jats:italic>‐lithiated arenes. Variable temperatures multinuclear magnetic resonance (<jats:sup>1</jats:sup>H, <jats:sup>7</jats:sup>Li, <jats:sup>13</jats:sup>C) mono‐ and two‐dimensional NMR studies and DFT computations supported the coexistence in solution of three chelated bridged dimeric aggregates, in slow equilibration at 180 K. The major isomer is an heterochiral aggregate on the basis of <jats:sup>1</jats:sup>H,<jats:sup>7</jats:sup>Li‐HOESY and <jats:sup>1</jats:sup>H,<jats:sup>1</jats:sup>H‐NOESY experiments. Conclusions were supported by the preparation of enantiomerically enriched (<jats:italic>S</jats:italic>)‐<jats:bold>1‐Li</jats:bold>. The privileged formation of homochiral aggregates from racemic mixtures may also have implications for the development of chiral resolution processes.</jats:p> |
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| author | Perna, Filippo M., Falcicchio, Aurelia, Salomone, Antonio, Milet, Anne, Rizzi, Rosanna, Hamdoun, Ghanem, Barozzino‐Consiglio, Gabriella, Stalke, Dietmar, Oulyadi, Hassan, Capriati, Vito |
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| description | <jats:p>Oxetanes are key synthons for asymmetric synthesis and also effective in directing <jats:italic>ortho</jats:italic>‐lithiation. This work first reports the solution and the solid‐state structure of an <jats:italic>ortho</jats:italic>‐lithiated aryloxetane (<jats:bold>1‐Li</jats:bold>) in the presence/absence of a bidentate ligand such as <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>,<jats:italic>N′</jats:italic>,<jats:italic>N′</jats:italic>‐tetramethylethylenediamine (TMEDA). Single crystal X‐ray diffraction analysis of <jats:bold>1‐Li</jats:bold> revealed a singular crystallographic structure in which the asymmetric unit comprises a core where the lithium atom is coordinated to the nitrogen atom of half a molecule of TMEDA and intramolecularly stabilised by the oxetane ring oxygen. This aggregation state is unprecedented in <jats:italic>ortho</jats:italic>‐lithiated arenes. Variable temperatures multinuclear magnetic resonance (<jats:sup>1</jats:sup>H, <jats:sup>7</jats:sup>Li, <jats:sup>13</jats:sup>C) mono‐ and two‐dimensional NMR studies and DFT computations supported the coexistence in solution of three chelated bridged dimeric aggregates, in slow equilibration at 180 K. The major isomer is an heterochiral aggregate on the basis of <jats:sup>1</jats:sup>H,<jats:sup>7</jats:sup>Li‐HOESY and <jats:sup>1</jats:sup>H,<jats:sup>1</jats:sup>H‐NOESY experiments. Conclusions were supported by the preparation of enantiomerically enriched (<jats:italic>S</jats:italic>)‐<jats:bold>1‐Li</jats:bold>. The privileged formation of homochiral aggregates from racemic mixtures may also have implications for the development of chiral resolution processes.</jats:p> |
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| spelling | Perna, Filippo M. Falcicchio, Aurelia Salomone, Antonio Milet, Anne Rizzi, Rosanna Hamdoun, Ghanem Barozzino‐Consiglio, Gabriella Stalke, Dietmar Oulyadi, Hassan Capriati, Vito 1434-193X 1099-0690 Wiley Organic Chemistry Physical and Theoretical Chemistry http://dx.doi.org/10.1002/ejoc.201900949 <jats:p>Oxetanes are key synthons for asymmetric synthesis and also effective in directing <jats:italic>ortho</jats:italic>‐lithiation. This work first reports the solution and the solid‐state structure of an <jats:italic>ortho</jats:italic>‐lithiated aryloxetane (<jats:bold>1‐Li</jats:bold>) in the presence/absence of a bidentate ligand such as <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>,<jats:italic>N′</jats:italic>,<jats:italic>N′</jats:italic>‐tetramethylethylenediamine (TMEDA). Single crystal X‐ray diffraction analysis of <jats:bold>1‐Li</jats:bold> revealed a singular crystallographic structure in which the asymmetric unit comprises a core where the lithium atom is coordinated to the nitrogen atom of half a molecule of TMEDA and intramolecularly stabilised by the oxetane ring oxygen. This aggregation state is unprecedented in <jats:italic>ortho</jats:italic>‐lithiated arenes. Variable temperatures multinuclear magnetic resonance (<jats:sup>1</jats:sup>H, <jats:sup>7</jats:sup>Li, <jats:sup>13</jats:sup>C) mono‐ and two‐dimensional NMR studies and DFT computations supported the coexistence in solution of three chelated bridged dimeric aggregates, in slow equilibration at 180 K. The major isomer is an heterochiral aggregate on the basis of <jats:sup>1</jats:sup>H,<jats:sup>7</jats:sup>Li‐HOESY and <jats:sup>1</jats:sup>H,<jats:sup>1</jats:sup>H‐NOESY experiments. Conclusions were supported by the preparation of enantiomerically enriched (<jats:italic>S</jats:italic>)‐<jats:bold>1‐Li</jats:bold>. The privileged formation of homochiral aggregates from racemic mixtures may also have implications for the development of chiral resolution processes.</jats:p> First Direct Evidence of an <i>ortho</i>‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics European Journal of Organic Chemistry |
| spellingShingle | Perna, Filippo M., Falcicchio, Aurelia, Salomone, Antonio, Milet, Anne, Rizzi, Rosanna, Hamdoun, Ghanem, Barozzino‐Consiglio, Gabriella, Stalke, Dietmar, Oulyadi, Hassan, Capriati, Vito, European Journal of Organic Chemistry, First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics, Organic Chemistry, Physical and Theoretical Chemistry |
| title | First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_full | First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_fullStr | First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_full_unstemmed | First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_short | First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| title_sort | first direct evidence of an <i>ortho</i>‐lithiated aryloxetane: solid and solution structure, and dynamics |
| title_unstemmed | First Direct Evidence of an ortho‐Lithiated Aryloxetane: Solid and Solution Structure, and Dynamics |
| topic | Organic Chemistry, Physical and Theoretical Chemistry |
| url | http://dx.doi.org/10.1002/ejoc.201900949 |