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A New Access to Chiral Phospholanes
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| Zeitschriftentitel: | European Journal of Organic Chemistry |
|---|---|
| Personen und Körperschaften: | , , , , , , , |
| In: | European Journal of Organic Chemistry, 2006, 2006, 15, S. 3412-3420 |
| Format: | E-Article |
| Sprache: | Englisch |
| veröffentlicht: |
Wiley
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| Schlagwörter: |
| author_facet |
Dubrovina, Natalia V. Jiao, Haijun Tararov, Vitali I. Spannenberg, Anke Kadyrov, Renat Monsees, Axel Christiansen, Andrea Börner, Armin Dubrovina, Natalia V. Jiao, Haijun Tararov, Vitali I. Spannenberg, Anke Kadyrov, Renat Monsees, Axel Christiansen, Andrea Börner, Armin |
|---|---|
| author |
Dubrovina, Natalia V. Jiao, Haijun Tararov, Vitali I. Spannenberg, Anke Kadyrov, Renat Monsees, Axel Christiansen, Andrea Börner, Armin |
| spellingShingle |
Dubrovina, Natalia V. Jiao, Haijun Tararov, Vitali I. Spannenberg, Anke Kadyrov, Renat Monsees, Axel Christiansen, Andrea Börner, Armin European Journal of Organic Chemistry A New Access to Chiral Phospholanes Organic Chemistry Physical and Theoretical Chemistry |
| author_sort |
dubrovina, natalia v. |
| spelling |
Dubrovina, Natalia V. Jiao, Haijun Tararov, Vitali I. Spannenberg, Anke Kadyrov, Renat Monsees, Axel Christiansen, Andrea Börner, Armin 1434-193X 1099-0690 Wiley Organic Chemistry Physical and Theoretical Chemistry http://dx.doi.org/10.1002/ejoc.200600143 <jats:title>Abstract</jats:title><jats:p>The hydrogenation of 5‐oxo‐5<jats:italic>H</jats:italic>‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol gives, almost quantitatively, only one geometric isomer of 5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>2</jats:bold>). An X‐ray structure analysis confirmed the formation of a <jats:italic>meso</jats:italic> isomer with a 4aβ,5aβ,9aβ,9bβ configuration (<jats:bold>2a</jats:bold>). Another possible way to get <jats:bold>2a</jats:bold> is the hydrogenation of (4aβ,5aβ)‐5‐oxo‐2,3,4,4a,5,5a,6,7,8,9‐decahydro‐1<jats:italic>H</jats:italic>‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>11</jats:bold>), which is easily available starting from cyclohexanone. Highly selective epimerization has been achieved using LDA as base at elevated temperature. Resolution of <jats:bold>2e</jats:bold> was achieved by salt formation with (<jats:italic>R</jats:italic>)‐(+)‐ and (<jats:italic>S</jats:italic>)‐(–)‐<jats:italic>N</jats:italic>‐benzyl‐α‐methylbenzylamine to give (+)‐ and (–)‐(4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol. The geometry of <jats:bold>2e</jats:bold> was confirmed by X‐ray structure analysis. Reduction of (+)‐ or (–)‐<jats:bold>2e</jats:bold> gave diastereomeric phospholanes (4aα,5<jats:italic>R</jats:italic>/<jats:italic>S</jats:italic>,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole (<jats:bold>1a</jats:bold>), which were oxidized to the corresponding secondary phosphane oxides (SPOs) (4aα,5<jats:italic>R</jats:italic>/<jats:italic>S</jats:italic>,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole 5‐oxide (<jats:bold>1b</jats:bold>). These phosphanes and phosphane oxides were used as ligands and preligands, respectively, in the Rh‐catalyzed enantioselective hydrogenation of benchmark substrates, where up to 79 % <jats:italic>ee</jats:italic> have been achieved. B3LYP density functional calculations reveal that among the three possible epimers at the <jats:sup>4a</jats:sup>C‐ and <jats:sup>5a</jats:sup>C‐positions the<jats:italic>chiral</jats:italic> isomer (4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>2e</jats:bold>) is 3.52 kcal mol<jats:sup>–1</jats:sup> more stable than the related <jats:italic>meso</jats:italic> isomer <jats:bold>2a</jats:bold> in Gibbs free energy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</jats:p> A New Access to Chiral Phospholanes European Journal of Organic Chemistry |
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10.1002/ejoc.200600143 |
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Chemie und Pharmazie Physik |
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Wiley, 2006 |
| imprint_str_mv |
Wiley, 2006 |
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1434-193X 1099-0690 |
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1434-193X 1099-0690 |
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English |
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Wiley (CrossRef) |
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2006 |
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Wiley |
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ai |
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ai |
| series |
European Journal of Organic Chemistry |
| source_id |
49 |
| title |
A New Access to Chiral Phospholanes |
| title_unstemmed |
A New Access to Chiral Phospholanes |
| title_full |
A New Access to Chiral Phospholanes |
| title_fullStr |
A New Access to Chiral Phospholanes |
| title_full_unstemmed |
A New Access to Chiral Phospholanes |
| title_short |
A New Access to Chiral Phospholanes |
| title_sort |
a new access to chiral phospholanes |
| topic |
Organic Chemistry Physical and Theoretical Chemistry |
| url |
http://dx.doi.org/10.1002/ejoc.200600143 |
| publishDate |
2006 |
| physical |
3412-3420 |
| description |
<jats:title>Abstract</jats:title><jats:p>The hydrogenation of 5‐oxo‐5<jats:italic>H</jats:italic>‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol gives, almost quantitatively, only one geometric isomer of 5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>2</jats:bold>). An X‐ray structure analysis confirmed the formation of a <jats:italic>meso</jats:italic> isomer with a 4aβ,5aβ,9aβ,9bβ configuration (<jats:bold>2a</jats:bold>). Another possible way to get <jats:bold>2a</jats:bold> is the hydrogenation of (4aβ,5aβ)‐5‐oxo‐2,3,4,4a,5,5a,6,7,8,9‐decahydro‐1<jats:italic>H</jats:italic>‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>11</jats:bold>), which is easily available starting from cyclohexanone. Highly selective epimerization has been achieved using LDA as base at elevated temperature. Resolution of <jats:bold>2e</jats:bold> was achieved by salt formation with (<jats:italic>R</jats:italic>)‐(+)‐ and (<jats:italic>S</jats:italic>)‐(–)‐<jats:italic>N</jats:italic>‐benzyl‐α‐methylbenzylamine to give (+)‐ and (–)‐(4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol. The geometry of <jats:bold>2e</jats:bold> was confirmed by X‐ray structure analysis. Reduction of (+)‐ or (–)‐<jats:bold>2e</jats:bold> gave diastereomeric phospholanes (4aα,5<jats:italic>R</jats:italic>/<jats:italic>S</jats:italic>,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole (<jats:bold>1a</jats:bold>), which were oxidized to the corresponding secondary phosphane oxides (SPOs) (4aα,5<jats:italic>R</jats:italic>/<jats:italic>S</jats:italic>,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole 5‐oxide (<jats:bold>1b</jats:bold>). These phosphanes and phosphane oxides were used as ligands and preligands, respectively, in the Rh‐catalyzed enantioselective hydrogenation of benchmark substrates, where up to 79 % <jats:italic>ee</jats:italic> have been achieved. B3LYP density functional calculations reveal that among the three possible epimers at the <jats:sup>4a</jats:sup>C‐ and <jats:sup>5a</jats:sup>C‐positions the<jats:italic>chiral</jats:italic> isomer (4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>2e</jats:bold>) is 3.52 kcal mol<jats:sup>–1</jats:sup> more stable than the related <jats:italic>meso</jats:italic> isomer <jats:bold>2a</jats:bold> in Gibbs free energy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</jats:p> |
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| author | Dubrovina, Natalia V., Jiao, Haijun, Tararov, Vitali I., Spannenberg, Anke, Kadyrov, Renat, Monsees, Axel, Christiansen, Andrea, Börner, Armin |
| author_facet | Dubrovina, Natalia V., Jiao, Haijun, Tararov, Vitali I., Spannenberg, Anke, Kadyrov, Renat, Monsees, Axel, Christiansen, Andrea, Börner, Armin, Dubrovina, Natalia V., Jiao, Haijun, Tararov, Vitali I., Spannenberg, Anke, Kadyrov, Renat, Monsees, Axel, Christiansen, Andrea, Börner, Armin |
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| description | <jats:title>Abstract</jats:title><jats:p>The hydrogenation of 5‐oxo‐5<jats:italic>H</jats:italic>‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol gives, almost quantitatively, only one geometric isomer of 5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>2</jats:bold>). An X‐ray structure analysis confirmed the formation of a <jats:italic>meso</jats:italic> isomer with a 4aβ,5aβ,9aβ,9bβ configuration (<jats:bold>2a</jats:bold>). Another possible way to get <jats:bold>2a</jats:bold> is the hydrogenation of (4aβ,5aβ)‐5‐oxo‐2,3,4,4a,5,5a,6,7,8,9‐decahydro‐1<jats:italic>H</jats:italic>‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>11</jats:bold>), which is easily available starting from cyclohexanone. Highly selective epimerization has been achieved using LDA as base at elevated temperature. Resolution of <jats:bold>2e</jats:bold> was achieved by salt formation with (<jats:italic>R</jats:italic>)‐(+)‐ and (<jats:italic>S</jats:italic>)‐(–)‐<jats:italic>N</jats:italic>‐benzyl‐α‐methylbenzylamine to give (+)‐ and (–)‐(4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol. The geometry of <jats:bold>2e</jats:bold> was confirmed by X‐ray structure analysis. Reduction of (+)‐ or (–)‐<jats:bold>2e</jats:bold> gave diastereomeric phospholanes (4aα,5<jats:italic>R</jats:italic>/<jats:italic>S</jats:italic>,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole (<jats:bold>1a</jats:bold>), which were oxidized to the corresponding secondary phosphane oxides (SPOs) (4aα,5<jats:italic>R</jats:italic>/<jats:italic>S</jats:italic>,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole 5‐oxide (<jats:bold>1b</jats:bold>). These phosphanes and phosphane oxides were used as ligands and preligands, respectively, in the Rh‐catalyzed enantioselective hydrogenation of benchmark substrates, where up to 79 % <jats:italic>ee</jats:italic> have been achieved. B3LYP density functional calculations reveal that among the three possible epimers at the <jats:sup>4a</jats:sup>C‐ and <jats:sup>5a</jats:sup>C‐positions the<jats:italic>chiral</jats:italic> isomer (4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>2e</jats:bold>) is 3.52 kcal mol<jats:sup>–1</jats:sup> more stable than the related <jats:italic>meso</jats:italic> isomer <jats:bold>2a</jats:bold> in Gibbs free energy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</jats:p> |
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| spelling | Dubrovina, Natalia V. Jiao, Haijun Tararov, Vitali I. Spannenberg, Anke Kadyrov, Renat Monsees, Axel Christiansen, Andrea Börner, Armin 1434-193X 1099-0690 Wiley Organic Chemistry Physical and Theoretical Chemistry http://dx.doi.org/10.1002/ejoc.200600143 <jats:title>Abstract</jats:title><jats:p>The hydrogenation of 5‐oxo‐5<jats:italic>H</jats:italic>‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol gives, almost quantitatively, only one geometric isomer of 5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>2</jats:bold>). An X‐ray structure analysis confirmed the formation of a <jats:italic>meso</jats:italic> isomer with a 4aβ,5aβ,9aβ,9bβ configuration (<jats:bold>2a</jats:bold>). Another possible way to get <jats:bold>2a</jats:bold> is the hydrogenation of (4aβ,5aβ)‐5‐oxo‐2,3,4,4a,5,5a,6,7,8,9‐decahydro‐1<jats:italic>H</jats:italic>‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>11</jats:bold>), which is easily available starting from cyclohexanone. Highly selective epimerization has been achieved using LDA as base at elevated temperature. Resolution of <jats:bold>2e</jats:bold> was achieved by salt formation with (<jats:italic>R</jats:italic>)‐(+)‐ and (<jats:italic>S</jats:italic>)‐(–)‐<jats:italic>N</jats:italic>‐benzyl‐α‐methylbenzylamine to give (+)‐ and (–)‐(4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol. The geometry of <jats:bold>2e</jats:bold> was confirmed by X‐ray structure analysis. Reduction of (+)‐ or (–)‐<jats:bold>2e</jats:bold> gave diastereomeric phospholanes (4aα,5<jats:italic>R</jats:italic>/<jats:italic>S</jats:italic>,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole (<jats:bold>1a</jats:bold>), which were oxidized to the corresponding secondary phosphane oxides (SPOs) (4aα,5<jats:italic>R</jats:italic>/<jats:italic>S</jats:italic>,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole 5‐oxide (<jats:bold>1b</jats:bold>). These phosphanes and phosphane oxides were used as ligands and preligands, respectively, in the Rh‐catalyzed enantioselective hydrogenation of benchmark substrates, where up to 79 % <jats:italic>ee</jats:italic> have been achieved. B3LYP density functional calculations reveal that among the three possible epimers at the <jats:sup>4a</jats:sup>C‐ and <jats:sup>5a</jats:sup>C‐positions the<jats:italic>chiral</jats:italic> isomer (4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ<jats:sup>5</jats:sup>‐dibenzophosphol‐5‐ol (<jats:bold>2e</jats:bold>) is 3.52 kcal mol<jats:sup>–1</jats:sup> more stable than the related <jats:italic>meso</jats:italic> isomer <jats:bold>2a</jats:bold> in Gibbs free energy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</jats:p> A New Access to Chiral Phospholanes European Journal of Organic Chemistry |
| spellingShingle | Dubrovina, Natalia V., Jiao, Haijun, Tararov, Vitali I., Spannenberg, Anke, Kadyrov, Renat, Monsees, Axel, Christiansen, Andrea, Börner, Armin, European Journal of Organic Chemistry, A New Access to Chiral Phospholanes, Organic Chemistry, Physical and Theoretical Chemistry |
| title | A New Access to Chiral Phospholanes |
| title_full | A New Access to Chiral Phospholanes |
| title_fullStr | A New Access to Chiral Phospholanes |
| title_full_unstemmed | A New Access to Chiral Phospholanes |
| title_short | A New Access to Chiral Phospholanes |
| title_sort | a new access to chiral phospholanes |
| title_unstemmed | A New Access to Chiral Phospholanes |
| topic | Organic Chemistry, Physical and Theoretical Chemistry |
| url | http://dx.doi.org/10.1002/ejoc.200600143 |