Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions.
Levulinic acid-derived 6-diazoheptane-2,5-dione (9) serves as a common precursor in a formal synthesis of frontalin 19, and in syntheses of cis-nemorensic acid 1, 4-hydroxy-cis-nemorensic acid 2, 3-hydroxy-cis-nemorensic acid 3, and nemorensic acid 4. The key step in these syntheses is the Rh(2)(OAc...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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2004
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| _version_ | 1826297543469826048 |
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| author | Hodgson, D Le Strat, F Avery, T Donohue, A Brückl, T |
| author_facet | Hodgson, D Le Strat, F Avery, T Donohue, A Brückl, T |
| author_sort | Hodgson, D |
| collection | OXFORD |
| description | Levulinic acid-derived 6-diazoheptane-2,5-dione (9) serves as a common precursor in a formal synthesis of frontalin 19, and in syntheses of cis-nemorensic acid 1, 4-hydroxy-cis-nemorensic acid 2, 3-hydroxy-cis-nemorensic acid 3, and nemorensic acid 4. The key step in these syntheses is the Rh(2)(OAc)(4)-catalyzed tandem carbonyl ylide formation-intermolecular 1,3-dipolar cycloadditions of diazodione 9 with formaldehyde, alkynes or allene, which occur with high regioselectivity. Subsequent oxidative cleavage of the ring originally derived from the cyclic carbonyl ylide intermediate provides a straightforward access to polysubstituted tetrahydrofurans, and in particular an efficient entry to the nemorensic acids. Enantioselective cycloadditions with diazodione 9, using chiral rhodium catalysts, gave cycloadducts in up to 51% ee. |
| first_indexed | 2024-03-07T04:33:14Z |
| format | Journal article |
| id | oxford-uuid:cf0a2e44-866a-41fc-8ad1-963f5931328e |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T04:33:14Z |
| publishDate | 2004 |
| record_format | dspace |
| spelling | oxford-uuid:cf0a2e44-866a-41fc-8ad1-963f5931328e2022-03-27T07:39:46ZStereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:cf0a2e44-866a-41fc-8ad1-963f5931328eEnglishSymplectic Elements at Oxford2004Hodgson, DLe Strat, FAvery, TDonohue, ABrückl, TLevulinic acid-derived 6-diazoheptane-2,5-dione (9) serves as a common precursor in a formal synthesis of frontalin 19, and in syntheses of cis-nemorensic acid 1, 4-hydroxy-cis-nemorensic acid 2, 3-hydroxy-cis-nemorensic acid 3, and nemorensic acid 4. The key step in these syntheses is the Rh(2)(OAc)(4)-catalyzed tandem carbonyl ylide formation-intermolecular 1,3-dipolar cycloadditions of diazodione 9 with formaldehyde, alkynes or allene, which occur with high regioselectivity. Subsequent oxidative cleavage of the ring originally derived from the cyclic carbonyl ylide intermediate provides a straightforward access to polysubstituted tetrahydrofurans, and in particular an efficient entry to the nemorensic acids. Enantioselective cycloadditions with diazodione 9, using chiral rhodium catalysts, gave cycloadducts in up to 51% ee. |
| spellingShingle | Hodgson, D Le Strat, F Avery, T Donohue, A Brückl, T Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions. |
| title | Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions. |
| title_full | Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions. |
| title_fullStr | Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions. |
| title_full_unstemmed | Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions. |
| title_short | Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions. |
| title_sort | stereocontrolled syntheses of the nemorensic acids using 6 diazoheptane 2 5 dione in carbonyl ylide cycloadditions |
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