Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanides
Ferrocenyl hetaryl thioketones react smoothly with in situ generated thiocarbonyl S-methanides to give 1,3-dithiolanes. In the case of aromatic S-methanides, the sterically more crowded 4,4,5,5-tetrasubstituted 1,3-dithiolanes (2-CH2 isomers) were formed as sole products. The reactions with cycloali...
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Beilstein-Institut
2016-07-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.12.136 |
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| author | Grzegorz Mlostoń Róża Hamera-Fałdyga Anthony Linden Heinz Heimgartner |
| author_facet | Grzegorz Mlostoń Róża Hamera-Fałdyga Anthony Linden Heinz Heimgartner |
| author_sort | Grzegorz Mlostoń |
| collection | DOAJ |
| description | Ferrocenyl hetaryl thioketones react smoothly with in situ generated thiocarbonyl S-methanides to give 1,3-dithiolanes. In the case of aromatic S-methanides, the sterically more crowded 4,4,5,5-tetrasubstituted 1,3-dithiolanes (2-CH2 isomers) were formed as sole products. The reactions with cycloaliphatic S-methanides led to mixtures of 2-CH2 and 5-CH2 isomers with the major component being the sterically more crowded 2-CH2 isomers. The preferred formation of the latter products is explained by the assumption that the formal [3 + 2]-cycloadducts were formed via a stepwise reaction mechanism with a stabilized 1,5-diradical as a key intermediate. The complete change of the reaction mechanism toward the concerted [3 + 2]-cycloaddition was observed in the reaction of a sterically crowded cycloaliphatic thiocarbonyl ylide with ferrocenyl methyl thioketone. |
| first_indexed | 2024-12-20T10:25:22Z |
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| id | doaj.art-d9e76b45c8b1498c8544e04ba15a3a49 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-20T10:25:22Z |
| publishDate | 2016-07-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-d9e76b45c8b1498c8544e04ba15a3a492022-12-21T19:43:51ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972016-07-011211421142710.3762/bjoc.12.1361860-5397-12-136Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanidesGrzegorz Mlostoń0Róża Hamera-Fałdyga1Anthony Linden2Heinz Heimgartner3Department of Organic and Applied Chemistry, University of Łódź, Tamka 12, PL 91-403 Łódź, PolandDepartment of Organic and Applied Chemistry, University of Łódź, Tamka 12, PL 91-403 Łódź, PolandDepartment of Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, SwitzerlandDepartment of Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, SwitzerlandFerrocenyl hetaryl thioketones react smoothly with in situ generated thiocarbonyl S-methanides to give 1,3-dithiolanes. In the case of aromatic S-methanides, the sterically more crowded 4,4,5,5-tetrasubstituted 1,3-dithiolanes (2-CH2 isomers) were formed as sole products. The reactions with cycloaliphatic S-methanides led to mixtures of 2-CH2 and 5-CH2 isomers with the major component being the sterically more crowded 2-CH2 isomers. The preferred formation of the latter products is explained by the assumption that the formal [3 + 2]-cycloadducts were formed via a stepwise reaction mechanism with a stabilized 1,5-diradical as a key intermediate. The complete change of the reaction mechanism toward the concerted [3 + 2]-cycloaddition was observed in the reaction of a sterically crowded cycloaliphatic thiocarbonyl ylide with ferrocenyl methyl thioketone.https://doi.org/10.3762/bjoc.12.136[3 + 2]-cycloadditions1,3-dithiolanesferrocenethiocarbonyl S-methanidesthioketones |
| spellingShingle | Grzegorz Mlostoń Róża Hamera-Fałdyga Anthony Linden Heinz Heimgartner Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanides Beilstein Journal of Organic Chemistry [3 + 2]-cycloadditions 1,3-dithiolanes ferrocene thiocarbonyl S-methanides thioketones |
| title | Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanides |
| title_full | Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanides |
| title_fullStr | Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanides |
| title_full_unstemmed | Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanides |
| title_short | Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanides |
| title_sort | synthesis of ferrocenyl substituted 1 3 dithiolanes via 3 2 cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl s methanides |
| topic | [3 + 2]-cycloadditions 1,3-dithiolanes ferrocene thiocarbonyl S-methanides thioketones |
| url | https://doi.org/10.3762/bjoc.12.136 |
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