Origin of diastereocontrol in the oxy-Michael reactions of delta-lactol anions: a computational and experimental study.
The diastereoselectivity in the alkylation and Michael addition of "naked" 6-substituted delta-lactolates has been studied by density functional (B3LYP) calculations with ab initio (MP2) energy refinements. The resulting proposed model for the origins of stereocontrol in this reaction has...
| Main Authors: | , , , |
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| 格式: | Journal article |
| 語言: | English |
| 出版: |
2008
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| _version_ | 1826300393179578368 |
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| author | Richardson, R Hernandez-Juan, F Ward, J Dixon, D |
| author_facet | Richardson, R Hernandez-Juan, F Ward, J Dixon, D |
| author_sort | Richardson, R |
| collection | OXFORD |
| description | The diastereoselectivity in the alkylation and Michael addition of "naked" 6-substituted delta-lactolates has been studied by density functional (B3LYP) calculations with ab initio (MP2) energy refinements. The resulting proposed model for the origins of stereocontrol in this reaction has been tested by experiment. The reactions lead to a high cis diastereoselectivity across the THP ring due to the preference for both the alkoxide and the 6-substituent to sit equatorial in the alkylation transition structure. In the oxy-Michael addition of these lactolates to beta-substituted nitroolefins, we propose that the high diastereoselectivity beta- to the nitro group is a result of a combination of steric, stereoelectronic and solvation factors. |
| first_indexed | 2024-03-07T05:16:29Z |
| format | Journal article |
| id | oxford-uuid:dd614d76-d070-48c8-a62e-92b96b87b91f |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T05:16:29Z |
| publishDate | 2008 |
| record_format | dspace |
| spelling | oxford-uuid:dd614d76-d070-48c8-a62e-92b96b87b91f2022-03-27T09:24:36ZOrigin of diastereocontrol in the oxy-Michael reactions of delta-lactol anions: a computational and experimental study.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:dd614d76-d070-48c8-a62e-92b96b87b91fEnglishSymplectic Elements at Oxford2008Richardson, RHernandez-Juan, FWard, JDixon, DThe diastereoselectivity in the alkylation and Michael addition of "naked" 6-substituted delta-lactolates has been studied by density functional (B3LYP) calculations with ab initio (MP2) energy refinements. The resulting proposed model for the origins of stereocontrol in this reaction has been tested by experiment. The reactions lead to a high cis diastereoselectivity across the THP ring due to the preference for both the alkoxide and the 6-substituent to sit equatorial in the alkylation transition structure. In the oxy-Michael addition of these lactolates to beta-substituted nitroolefins, we propose that the high diastereoselectivity beta- to the nitro group is a result of a combination of steric, stereoelectronic and solvation factors. |
| spellingShingle | Richardson, R Hernandez-Juan, F Ward, J Dixon, D Origin of diastereocontrol in the oxy-Michael reactions of delta-lactol anions: a computational and experimental study. |
| title | Origin of diastereocontrol in the oxy-Michael reactions of delta-lactol anions: a computational and experimental study. |
| title_full | Origin of diastereocontrol in the oxy-Michael reactions of delta-lactol anions: a computational and experimental study. |
| title_fullStr | Origin of diastereocontrol in the oxy-Michael reactions of delta-lactol anions: a computational and experimental study. |
| title_full_unstemmed | Origin of diastereocontrol in the oxy-Michael reactions of delta-lactol anions: a computational and experimental study. |
| title_short | Origin of diastereocontrol in the oxy-Michael reactions of delta-lactol anions: a computational and experimental study. |
| title_sort | origin of diastereocontrol in the oxy michael reactions of delta lactol anions a computational and experimental study |
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