Diastereoselective Synthesis of <i>cis</i>-2,6-Disubstituted Dihydropyrane Derivatives through a Competitive Silyl-Prins Cyclization versus Alternative Reaction Pathways
A convenient regioselective synthesis of allyl- and vinylsilyl alcohols, from a common precursor, was described, by selecting the appropriate reaction conditions. Allyl- and vinylsilyl alcohols were tested in silyl-Prins cyclizations for the preparation of disubstituted oxygenated heterocycles in a...
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| Format: | Article |
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MDPI AG
2023-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/7/3080 |
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| author | Laura F. Peña Enol López Ángel Sánchez-González Asunción Barbero |
| author_facet | Laura F. Peña Enol López Ángel Sánchez-González Asunción Barbero |
| author_sort | Laura F. Peña |
| collection | DOAJ |
| description | A convenient regioselective synthesis of allyl- and vinylsilyl alcohols, from a common precursor, was described, by selecting the appropriate reaction conditions. Allyl- and vinylsilyl alcohols were tested in silyl-Prins cyclizations for the preparation of disubstituted oxygenated heterocycles in a one-pot sequential reaction. The methodology was sensitive to the structure of the starting alkenylsilyl alcohol and reaction conditions, with competitive pathways observed (particularly for allylsilyl alcohols), such as Peterson elimination and oxonia-Cope reactions. However, the use of vinylsilyl alcohols allowed the preparation of differently disubstituted <i>cis</i>-2,6-dihydropyrans in moderate to good yields. Computational studies support the proposed mechanism. |
| first_indexed | 2024-03-11T05:29:33Z |
| format | Article |
| id | doaj.art-40663a2d2d2842019edd3b5809c59740 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T05:29:33Z |
| publishDate | 2023-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-40663a2d2d2842019edd3b5809c597402023-11-17T17:13:13ZengMDPI AGMolecules1420-30492023-03-01287308010.3390/molecules28073080Diastereoselective Synthesis of <i>cis</i>-2,6-Disubstituted Dihydropyrane Derivatives through a Competitive Silyl-Prins Cyclization versus Alternative Reaction PathwaysLaura F. Peña0Enol López1Ángel Sánchez-González2Asunción Barbero3Department of Organic Chemistry, Campus Miguel Delibes, University of Valladolid, 47011 Valladolid, SpainDepartment of Organic Chemistry, Campus Miguel Delibes, University of Valladolid, 47011 Valladolid, SpainDepartment of Organic Chemistry, Campus Miguel Delibes, University of Valladolid, 47011 Valladolid, SpainDepartment of Organic Chemistry, Campus Miguel Delibes, University of Valladolid, 47011 Valladolid, SpainA convenient regioselective synthesis of allyl- and vinylsilyl alcohols, from a common precursor, was described, by selecting the appropriate reaction conditions. Allyl- and vinylsilyl alcohols were tested in silyl-Prins cyclizations for the preparation of disubstituted oxygenated heterocycles in a one-pot sequential reaction. The methodology was sensitive to the structure of the starting alkenylsilyl alcohol and reaction conditions, with competitive pathways observed (particularly for allylsilyl alcohols), such as Peterson elimination and oxonia-Cope reactions. However, the use of vinylsilyl alcohols allowed the preparation of differently disubstituted <i>cis</i>-2,6-dihydropyrans in moderate to good yields. Computational studies support the proposed mechanism.https://www.mdpi.com/1420-3049/28/7/3080Prins cyclizationheterocyclesoxacycles |
| spellingShingle | Laura F. Peña Enol López Ángel Sánchez-González Asunción Barbero Diastereoselective Synthesis of <i>cis</i>-2,6-Disubstituted Dihydropyrane Derivatives through a Competitive Silyl-Prins Cyclization versus Alternative Reaction Pathways Molecules Prins cyclization heterocycles oxacycles |
| title | Diastereoselective Synthesis of <i>cis</i>-2,6-Disubstituted Dihydropyrane Derivatives through a Competitive Silyl-Prins Cyclization versus Alternative Reaction Pathways |
| title_full | Diastereoselective Synthesis of <i>cis</i>-2,6-Disubstituted Dihydropyrane Derivatives through a Competitive Silyl-Prins Cyclization versus Alternative Reaction Pathways |
| title_fullStr | Diastereoselective Synthesis of <i>cis</i>-2,6-Disubstituted Dihydropyrane Derivatives through a Competitive Silyl-Prins Cyclization versus Alternative Reaction Pathways |
| title_full_unstemmed | Diastereoselective Synthesis of <i>cis</i>-2,6-Disubstituted Dihydropyrane Derivatives through a Competitive Silyl-Prins Cyclization versus Alternative Reaction Pathways |
| title_short | Diastereoselective Synthesis of <i>cis</i>-2,6-Disubstituted Dihydropyrane Derivatives through a Competitive Silyl-Prins Cyclization versus Alternative Reaction Pathways |
| title_sort | diastereoselective synthesis of i cis i 2 6 disubstituted dihydropyrane derivatives through a competitive silyl prins cyclization versus alternative reaction pathways |
| topic | Prins cyclization heterocycles oxacycles |
| url | https://www.mdpi.com/1420-3049/28/7/3080 |
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