Intramolecular Diels-Alder reactions of cycloalkenones: stereoselectivity, Lewis acid acceleration, and halogen substituent effects.
The intramolecular Diels-Alder reactions of cycloalkenones and terminal dienes occur with high endo stereoselectivity, both thermally and under Lewis-acidic conditions. Through computations, we show that steric repulsion and tether conformation govern the selectivity of the reaction, and incorporati...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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2014
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| _version_ | 1797094800117202944 |
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| author | Pham, H Paton, R Ross, A Danishefsky, S Houk, K |
| author_facet | Pham, H Paton, R Ross, A Danishefsky, S Houk, K |
| author_sort | Pham, H |
| collection | OXFORD |
| description | The intramolecular Diels-Alder reactions of cycloalkenones and terminal dienes occur with high endo stereoselectivity, both thermally and under Lewis-acidic conditions. Through computations, we show that steric repulsion and tether conformation govern the selectivity of the reaction, and incorporation of either BF3 or α-halogenation increases the rate of cycloaddition. With a longer tether, isomerization from a terminal diene to the more stable internal diene results in a more facile cycloaddition. |
| first_indexed | 2024-03-07T04:19:01Z |
| format | Journal article |
| id | oxford-uuid:ca5f86f1-8b17-4c71-970f-6f626273fe5c |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T04:19:01Z |
| publishDate | 2014 |
| record_format | dspace |
| spelling | oxford-uuid:ca5f86f1-8b17-4c71-970f-6f626273fe5c2022-03-27T07:06:57ZIntramolecular Diels-Alder reactions of cycloalkenones: stereoselectivity, Lewis acid acceleration, and halogen substituent effects.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:ca5f86f1-8b17-4c71-970f-6f626273fe5cEnglishSymplectic Elements at Oxford2014Pham, HPaton, RRoss, ADanishefsky, SHouk, KThe intramolecular Diels-Alder reactions of cycloalkenones and terminal dienes occur with high endo stereoselectivity, both thermally and under Lewis-acidic conditions. Through computations, we show that steric repulsion and tether conformation govern the selectivity of the reaction, and incorporation of either BF3 or α-halogenation increases the rate of cycloaddition. With a longer tether, isomerization from a terminal diene to the more stable internal diene results in a more facile cycloaddition. |
| spellingShingle | Pham, H Paton, R Ross, A Danishefsky, S Houk, K Intramolecular Diels-Alder reactions of cycloalkenones: stereoselectivity, Lewis acid acceleration, and halogen substituent effects. |
| title | Intramolecular Diels-Alder reactions of cycloalkenones: stereoselectivity, Lewis acid acceleration, and halogen substituent effects. |
| title_full | Intramolecular Diels-Alder reactions of cycloalkenones: stereoselectivity, Lewis acid acceleration, and halogen substituent effects. |
| title_fullStr | Intramolecular Diels-Alder reactions of cycloalkenones: stereoselectivity, Lewis acid acceleration, and halogen substituent effects. |
| title_full_unstemmed | Intramolecular Diels-Alder reactions of cycloalkenones: stereoselectivity, Lewis acid acceleration, and halogen substituent effects. |
| title_short | Intramolecular Diels-Alder reactions of cycloalkenones: stereoselectivity, Lewis acid acceleration, and halogen substituent effects. |
| title_sort | intramolecular diels alder reactions of cycloalkenones stereoselectivity lewis acid acceleration and halogen substituent effects |
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