A catalytic asymmetric bioorganic route to enantioenriched tetrahydro- and dihydropyranones.
A conceptually novel approach to hetero Diels-Alder adducts of carbonyl compounds is described using as the key steps an antibody-mediated kinetic resolution of hydroxyenones followed by a ring-closure process. Various beta-hydroxyenones proved to be very good substrates for antibodies 84G3- and 93F...
| Main Authors: | , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
2005
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| _version_ | 1797091170325626880 |
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| author | Baker-Glenn, C Hodnett, N Reiter, M Ropp, S Ancliff, R Gouverneur, V |
| author_facet | Baker-Glenn, C Hodnett, N Reiter, M Ropp, S Ancliff, R Gouverneur, V |
| author_sort | Baker-Glenn, C |
| collection | OXFORD |
| description | A conceptually novel approach to hetero Diels-Alder adducts of carbonyl compounds is described using as the key steps an antibody-mediated kinetic resolution of hydroxyenones followed by a ring-closure process. Various beta-hydroxyenones proved to be very good substrates for antibodies 84G3- and 93F3-catalyzed retro-aldol reactions, allowing the preparation of highly enantiomerically enriched (up to 99% ee) precursors of pyranones. An attractive feature of this methodology is the possibility to convert these acyclic-enantioenriched beta-hydroxyenones into tetrahydropyranones by a conventional Michael-type addition procedure or into the corresponding dihydropyranones using an alternative palladium-catalyzed oxidative ring closure. For the palladium-mediated cyclization, a biphasic system has been implemented that allows the direct preparation of enantiopure dihydropyranones from the corresponding racemic aldol precursors using a sequential antibody-resolution/palladium-cyclization strategy, without isolation of the intermediate enantioenriched hydroxyenones. This bioorganic route is best applied to the preparation of hetero Diels-Alder adducts otherwise derived from less nucleophilic dienes and unactivated dienophiles. |
| first_indexed | 2024-03-07T03:29:12Z |
| format | Journal article |
| id | oxford-uuid:ba1aa452-44e8-44ae-a1fe-455e3d307b29 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T03:29:12Z |
| publishDate | 2005 |
| record_format | dspace |
| spelling | oxford-uuid:ba1aa452-44e8-44ae-a1fe-455e3d307b292022-03-27T05:07:41ZA catalytic asymmetric bioorganic route to enantioenriched tetrahydro- and dihydropyranones.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:ba1aa452-44e8-44ae-a1fe-455e3d307b29EnglishSymplectic Elements at Oxford2005Baker-Glenn, CHodnett, NReiter, MRopp, SAncliff, RGouverneur, VA conceptually novel approach to hetero Diels-Alder adducts of carbonyl compounds is described using as the key steps an antibody-mediated kinetic resolution of hydroxyenones followed by a ring-closure process. Various beta-hydroxyenones proved to be very good substrates for antibodies 84G3- and 93F3-catalyzed retro-aldol reactions, allowing the preparation of highly enantiomerically enriched (up to 99% ee) precursors of pyranones. An attractive feature of this methodology is the possibility to convert these acyclic-enantioenriched beta-hydroxyenones into tetrahydropyranones by a conventional Michael-type addition procedure or into the corresponding dihydropyranones using an alternative palladium-catalyzed oxidative ring closure. For the palladium-mediated cyclization, a biphasic system has been implemented that allows the direct preparation of enantiopure dihydropyranones from the corresponding racemic aldol precursors using a sequential antibody-resolution/palladium-cyclization strategy, without isolation of the intermediate enantioenriched hydroxyenones. This bioorganic route is best applied to the preparation of hetero Diels-Alder adducts otherwise derived from less nucleophilic dienes and unactivated dienophiles. |
| spellingShingle | Baker-Glenn, C Hodnett, N Reiter, M Ropp, S Ancliff, R Gouverneur, V A catalytic asymmetric bioorganic route to enantioenriched tetrahydro- and dihydropyranones. |
| title | A catalytic asymmetric bioorganic route to enantioenriched tetrahydro- and dihydropyranones. |
| title_full | A catalytic asymmetric bioorganic route to enantioenriched tetrahydro- and dihydropyranones. |
| title_fullStr | A catalytic asymmetric bioorganic route to enantioenriched tetrahydro- and dihydropyranones. |
| title_full_unstemmed | A catalytic asymmetric bioorganic route to enantioenriched tetrahydro- and dihydropyranones. |
| title_short | A catalytic asymmetric bioorganic route to enantioenriched tetrahydro- and dihydropyranones. |
| title_sort | catalytic asymmetric bioorganic route to enantioenriched tetrahydro and dihydropyranones |
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