Clarke, Paul A. orcid.org/0000-0003-3952-359X, Nasir, Nadiah Mad, Sellars, Philip B. et al. (3 more authors) (2016) Synthesis of 2,6-trans- and 3,3,6-Trisubstituted Tetrahydropyran-4-ones from Maitland-Japp Derived 2H-Dihydropyran-4-ones: A Total Synthesis of Diospongin B. Organic and Biomolecular Chemistry. pp. 6840-6852. ISSN 1477-0539
Abstract
6-Substituted-2H-dihydropyran-4-one products of the Maitland-Japp reaction have been converted into tetrahydropyrans containing uncommon substitution patterns. Treatment of 6-substituted-2H-dihydropyran-4-ones with carbon nucleophiles led to the formation of tetrahydropyran rings with the 2,6-trans-stereochemical arrangement. Reaction of the same 6-substituted-2H-dihydropyran-4-ones with l-Selectride led to the formation of 3,6-disubstituted tetrahydropyran rings, while trapping of the intermediate enolate with carbon electrophiles in turn led to the formation 3,3,6-trisubstituted tetrahydropyran rings. The relative stereochemical configuration of the new substituents was controlled by the stereoelectronic preference for pseudo-axial addition of the nucleophile and trapping of the enolate from the opposite face. Application of these methods led to a synthesis of the potent anti-osteoporotic diarylheptanoid natural product diospongin B.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry, 2016. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 24 Jun 2016 10:07 |
Last Modified: | 08 Feb 2025 00:19 |
Published Version: | https://doi.org/10.1039/C6OB01182A |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1039/C6OB01182A |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:101234 |
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