Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (<i>R</i>,<i>R</i>)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State
The resolution of racemic 1-phenylphosphin-2-en-4-one 1-oxide (<b>2</b>), was achieved through the fractional crystallization of its diastereomeric complexes with (4<i>R</i>,5<i>R</i>)-(−)-2,2-dimethyl -α,α,α′,α′-tetraphenyl-dioxolan-4,5-dimethanol (<i>R,R&l...
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2021
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oai:doaj.org-article:eb5dc90824cf4b1387c8507a7284a9172021-11-25T18:28:00ZResolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (<i>R</i>,<i>R</i>)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State10.3390/molecules262268731420-3049https://doaj.org/article/eb5dc90824cf4b1387c8507a7284a9172021-11-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/22/6873https://doaj.org/toc/1420-3049The resolution of racemic 1-phenylphosphin-2-en-4-one 1-oxide (<b>2</b>), was achieved through the fractional crystallization of its diastereomeric complexes with (4<i>R</i>,5<i>R</i>)-(−)-2,2-dimethyl -α,α,α′,α′-tetraphenyl-dioxolan-4,5-dimethanol (<i>R,R</i>-TADDOL) followed by the liberation of the individual enantiomers of <b>2</b> by flash chromatography on silica gel columns. The resolution process furnished the two enantiomers of <b>2</b> of 99.1 and 99.9% e.e. at isolated yields of 62 and 59% (counted for the single enantiomer), respectively. The absolute configurations of the two enantiomers were established by means of X-ray crystallography of their diastereomerically pure complexes, i.e., (<i>R</i>)-<b>2</b>•<i>R</i>,<i>R</i>)-TADDOL and (<i>S</i>)<i>-</i><b>2</b>•(<i>R</i>,<i>R</i>)-TADDOL. The structural analysis revealed that in the (<i>R</i>)-<b>2</b>•(<i>R</i>,<i>R</i>)-TADDOL complex, the P-phenyl substituent occupied a pseudoequatorial position, whereas in (<i>S</i>)-<b>2</b>•(<i>R</i>,<i>R</i>)-TADDOL, it appeared in both the pseudoequatorial and the pseudoaxial positions in four symmetrically independent molecules. Concurrent conformational changes of the TADDOL molecules were best described by the observed changes of a pseudo-torsional CO...OC angle that could be considered as a possible measure of TADDOL conformation in its receptor–ligand complexes. The structural analysis of the (<i>R</i>,<i>R</i>)-TADDOL molecule revealed that efficiency of this compound for use as an effective resolving factor comes from its ability to flexibly fit its structure to both enantiomers of a ligand molecule, producing a rare case of resolution for both pure enantiomers with one chiral separating agent. The resolved (<i>R</i>)-<b>2</b> was used to assign the absolute configuration of a recently described (−)-1-phenylphosphin-2-en-4-one 1-sulfide by chemical correlation. In addition, an attempted stereoretentive reduction of (<i>R</i>)-<b>2</b> by PhSiH<sub>3</sub> at 60 °C revealed an unexpectedly low barrier for P-inversion in 1-phenylphosphin-2-en-4-one.Elżbieta ŁastawieckaAdam WłodarczykAnna E. KoziołHanna MałuszyńskaK. Michał PietrusiewiczMDPI AGarticleP-stereogenicityphosphinanes1-phenylphosphin-2-en-4-one 1-oxidesix-membered carbon-phosphorus heterocyclesresolutionabsolute configurationOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6873, p 6873 (2021) |
| institution |
DOAJ |
| collection |
DOAJ |
| language |
EN |
| topic |
P-stereogenicity phosphinanes 1-phenylphosphin-2-en-4-one 1-oxide six-membered carbon-phosphorus heterocycles resolution absolute configuration Organic chemistry QD241-441 |
| spellingShingle |
P-stereogenicity phosphinanes 1-phenylphosphin-2-en-4-one 1-oxide six-membered carbon-phosphorus heterocycles resolution absolute configuration Organic chemistry QD241-441 Elżbieta Łastawiecka Adam Włodarczyk Anna E. Kozioł Hanna Małuszyńska K. Michał Pietrusiewicz Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (<i>R</i>,<i>R</i>)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State |
| description |
The resolution of racemic 1-phenylphosphin-2-en-4-one 1-oxide (<b>2</b>), was achieved through the fractional crystallization of its diastereomeric complexes with (4<i>R</i>,5<i>R</i>)-(−)-2,2-dimethyl -α,α,α′,α′-tetraphenyl-dioxolan-4,5-dimethanol (<i>R,R</i>-TADDOL) followed by the liberation of the individual enantiomers of <b>2</b> by flash chromatography on silica gel columns. The resolution process furnished the two enantiomers of <b>2</b> of 99.1 and 99.9% e.e. at isolated yields of 62 and 59% (counted for the single enantiomer), respectively. The absolute configurations of the two enantiomers were established by means of X-ray crystallography of their diastereomerically pure complexes, i.e., (<i>R</i>)-<b>2</b>•<i>R</i>,<i>R</i>)-TADDOL and (<i>S</i>)<i>-</i><b>2</b>•(<i>R</i>,<i>R</i>)-TADDOL. The structural analysis revealed that in the (<i>R</i>)-<b>2</b>•(<i>R</i>,<i>R</i>)-TADDOL complex, the P-phenyl substituent occupied a pseudoequatorial position, whereas in (<i>S</i>)-<b>2</b>•(<i>R</i>,<i>R</i>)-TADDOL, it appeared in both the pseudoequatorial and the pseudoaxial positions in four symmetrically independent molecules. Concurrent conformational changes of the TADDOL molecules were best described by the observed changes of a pseudo-torsional CO...OC angle that could be considered as a possible measure of TADDOL conformation in its receptor–ligand complexes. The structural analysis of the (<i>R</i>,<i>R</i>)-TADDOL molecule revealed that efficiency of this compound for use as an effective resolving factor comes from its ability to flexibly fit its structure to both enantiomers of a ligand molecule, producing a rare case of resolution for both pure enantiomers with one chiral separating agent. The resolved (<i>R</i>)-<b>2</b> was used to assign the absolute configuration of a recently described (−)-1-phenylphosphin-2-en-4-one 1-sulfide by chemical correlation. In addition, an attempted stereoretentive reduction of (<i>R</i>)-<b>2</b> by PhSiH<sub>3</sub> at 60 °C revealed an unexpectedly low barrier for P-inversion in 1-phenylphosphin-2-en-4-one. |
| format |
article |
| author |
Elżbieta Łastawiecka Adam Włodarczyk Anna E. Kozioł Hanna Małuszyńska K. Michał Pietrusiewicz |
| author_facet |
Elżbieta Łastawiecka Adam Włodarczyk Anna E. Kozioł Hanna Małuszyńska K. Michał Pietrusiewicz |
| author_sort |
Elżbieta Łastawiecka |
| title |
Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (<i>R</i>,<i>R</i>)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State |
| title_short |
Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (<i>R</i>,<i>R</i>)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State |
| title_full |
Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (<i>R</i>,<i>R</i>)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State |
| title_fullStr |
Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (<i>R</i>,<i>R</i>)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State |
| title_full_unstemmed |
Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (<i>R</i>,<i>R</i>)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State |
| title_sort |
resolution of p-sterogenic 1-phenylphosphin-2-en-4-one 1-oxide into two enantiomers by (<i>r</i>,<i>r</i>)-taddol and conformational diversity of the phosphinenone ring and taddol in the crystal state |
| publisher |
MDPI AG |
| publishDate |
2021 |
| url |
https://doaj.org/article/eb5dc90824cf4b1387c8507a7284a917 |
| work_keys_str_mv |
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