Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation
The three possible dimethylsubstituted phenyloxiranes (cis, trans and geminal) were synthesized in both racemic (mCPBA) and enantiomerically enriched forms (Shi epoxidation) and subjected to a vibrational circular dichroism study. The experimental spectra were compared to theoretical spectra obtaine...
| Main Authors: | , , , |
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| Format: | Journal Article |
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Springer Berlin
2008
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| Online Access: | http://hdl.handle.net/20.500.11937/45018 |
| _version_ | 1848757165490176000 |
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| author | Fristrup, P. Lassen, P. Tanner, D. Jalkanen, Karl |
| author_facet | Fristrup, P. Lassen, P. Tanner, D. Jalkanen, Karl |
| author_sort | Fristrup, P. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The three possible dimethylsubstituted phenyloxiranes (cis, trans and geminal) were synthesized in both racemic (mCPBA) and enantiomerically enriched forms (Shi epoxidation) and subjected to a vibrational circular dichroism study. The experimental spectra were compared to theoretical spectra obtained using DFT/B3LYP calculations, and the differences between experiment and theory are discussed. The absolute configuration at the benzylic position was established as being (R), (S) and (R) for the cis, trans and geminal dimethylsubstituted phenyloxiranes, respectively. In all three cases the configuration of the major enantiomer was in accordance with a simple transition state model based on the spiro reaction mode. |
| first_indexed | 2025-11-14T09:23:45Z |
| format | Journal Article |
| id | curtin-20.500.11937-45018 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T09:23:45Z |
| publishDate | 2008 |
| publisher | Springer Berlin |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-450182018-03-29T09:07:34Z Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation Fristrup, P. Lassen, P. Tanner, D. Jalkanen, Karl DFT calculations Epoxidation Vibrational circular dichroism Absolute configuration Asymmetric catalysis The three possible dimethylsubstituted phenyloxiranes (cis, trans and geminal) were synthesized in both racemic (mCPBA) and enantiomerically enriched forms (Shi epoxidation) and subjected to a vibrational circular dichroism study. The experimental spectra were compared to theoretical spectra obtained using DFT/B3LYP calculations, and the differences between experiment and theory are discussed. The absolute configuration at the benzylic position was established as being (R), (S) and (R) for the cis, trans and geminal dimethylsubstituted phenyloxiranes, respectively. In all three cases the configuration of the major enantiomer was in accordance with a simple transition state model based on the spiro reaction mode. 2008 Journal Article http://hdl.handle.net/20.500.11937/45018 10.1007/s00214-006-0186-1 Springer Berlin restricted |
| spellingShingle | DFT calculations Epoxidation Vibrational circular dichroism Absolute configuration Asymmetric catalysis Fristrup, P. Lassen, P. Tanner, D. Jalkanen, Karl Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation |
| title | Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation |
| title_full | Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation |
| title_fullStr | Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation |
| title_full_unstemmed | Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation |
| title_short | Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation |
| title_sort | direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by shi epoxidation |
| topic | DFT calculations Epoxidation Vibrational circular dichroism Absolute configuration Asymmetric catalysis |
| url | http://hdl.handle.net/20.500.11937/45018 |