Synthesis of (−)-6,7-dideoxysqualestatin H5 by carbonyl ylide cycloaddition–rearrangement and cross-electrophile coupling
An asymmetric synthesis of (−)-6,7-dideoxysqualestatin H5 is reported. Key features of the synthesis include: (1) highly diastereoselective n-alkylation of a tartrate acetonide enolate and subsequent oxidation−hydrolysis to provide an asymmetric entry to a β-hydroxy-α-ketoester motif; (2) facilitati...
| Auteurs principaux: | , , , , |
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| Format: | Journal article |
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American Chemical Society
2017
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| _version_ | 1826281654143942656 |
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| author | Fegheh-Hassanpour, Y Arif, T Sintim, H Al Mamari, H Hodgson, D |
| author_facet | Fegheh-Hassanpour, Y Arif, T Sintim, H Al Mamari, H Hodgson, D |
| author_sort | Fegheh-Hassanpour, Y |
| collection | OXFORD |
| description | An asymmetric synthesis of (−)-6,7-dideoxysqualestatin H5 is reported. Key features of the synthesis include: (1) highly diastereoselective n-alkylation of a tartrate acetonide enolate and subsequent oxidation−hydrolysis to provide an asymmetric entry to a β-hydroxy-α-ketoester motif; (2) facilitation of Rh(II)-catalyzed cyclic carbonyl ylide formation−cycloaddition by cogeneration of keto and diazo functionality through ozonolysis of an unsaturated hydrazone; and (3) stereoretentive Ni-catalyzed Csp<sup>3</sup>−Csp<sup>2</sup> cross-electrophile coupling between tricarboxylate core and unsaturated side-chain to complete the natural product. |
| first_indexed | 2024-03-07T00:32:03Z |
| format | Journal article |
| id | oxford-uuid:8023d4d7-1826-437a-a6ab-99c25524cd3c |
| institution | University of Oxford |
| last_indexed | 2024-03-07T00:32:03Z |
| publishDate | 2017 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:8023d4d7-1826-437a-a6ab-99c25524cd3c2022-03-26T21:21:23ZSynthesis of (−)-6,7-dideoxysqualestatin H5 by carbonyl ylide cycloaddition–rearrangement and cross-electrophile couplingJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:8023d4d7-1826-437a-a6ab-99c25524cd3cSymplectic Elements at OxfordAmerican Chemical Society2017Fegheh-Hassanpour, YArif, TSintim, HAl Mamari, HHodgson, DAn asymmetric synthesis of (−)-6,7-dideoxysqualestatin H5 is reported. Key features of the synthesis include: (1) highly diastereoselective n-alkylation of a tartrate acetonide enolate and subsequent oxidation−hydrolysis to provide an asymmetric entry to a β-hydroxy-α-ketoester motif; (2) facilitation of Rh(II)-catalyzed cyclic carbonyl ylide formation−cycloaddition by cogeneration of keto and diazo functionality through ozonolysis of an unsaturated hydrazone; and (3) stereoretentive Ni-catalyzed Csp<sup>3</sup>−Csp<sup>2</sup> cross-electrophile coupling between tricarboxylate core and unsaturated side-chain to complete the natural product. |
| spellingShingle | Fegheh-Hassanpour, Y Arif, T Sintim, H Al Mamari, H Hodgson, D Synthesis of (−)-6,7-dideoxysqualestatin H5 by carbonyl ylide cycloaddition–rearrangement and cross-electrophile coupling |
| title | Synthesis of (−)-6,7-dideoxysqualestatin H5 by carbonyl ylide cycloaddition–rearrangement and cross-electrophile coupling |
| title_full | Synthesis of (−)-6,7-dideoxysqualestatin H5 by carbonyl ylide cycloaddition–rearrangement and cross-electrophile coupling |
| title_fullStr | Synthesis of (−)-6,7-dideoxysqualestatin H5 by carbonyl ylide cycloaddition–rearrangement and cross-electrophile coupling |
| title_full_unstemmed | Synthesis of (−)-6,7-dideoxysqualestatin H5 by carbonyl ylide cycloaddition–rearrangement and cross-electrophile coupling |
| title_short | Synthesis of (−)-6,7-dideoxysqualestatin H5 by carbonyl ylide cycloaddition–rearrangement and cross-electrophile coupling |
| title_sort | synthesis of 6 7 dideoxysqualestatin h5 by carbonyl ylide cycloaddition rearrangement and cross electrophile coupling |
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