Convenient Synthesis of Thiohydantoins, Imidazole-2-thiones and Imidazo[2,1-b]thiazol-4-iums from Polymer-Supported α-Acylamino Ketones
The preparation of 5-methylene-thiohydantoins using solid-phase synthesis is reported in this paper. After sulfonylation of immobilized Ser (t-Bu)-OH with 4-nitrobenzenesulfonyl chloride followed by alkylation with various bromoketones, the 4-Nos group was removed and the resulting polymer-supported...
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doaj-94da5e641b1f4944ac51bd3fcd78c3a32020-11-24T22:26:45ZengMDPI AGMolecules1420-30492018-04-0123497610.3390/molecules23040976molecules23040976Convenient Synthesis of Thiohydantoins, Imidazole-2-thiones and Imidazo[2,1-b]thiazol-4-iums from Polymer-Supported α-Acylamino KetonesPetra Králová0Michal Maloň1Hiroyuki Koshino2Miroslav Soural3Department of Organic Chemistry, Faculty of Science, Palacký University, 17. Listopadu 12, 771 46 Olomouc, Czech RepublicJEOL Ltd., Musashino 3-1-2, Akishima, Tokyo 196-8558, JapanRIKEN Center for Sustainable Resource Science, Hirosawa 2-1, Wako, Saitama 351-0198, JapanInstitute of Molecular and Translational Medicine, Faculty of Medicine and Dentistry, Palacký University, Hnevotinska 5, 779 00 Olomouc, Czech RepublicThe preparation of 5-methylene-thiohydantoins using solid-phase synthesis is reported in this paper. After sulfonylation of immobilized Ser (t-Bu)-OH with 4-nitrobenzenesulfonyl chloride followed by alkylation with various bromoketones, the 4-Nos group was removed and the resulting polymer-supported α-acylamino ketones reacted with Fmoc-isothiocyanate. Cleavage of the Fmoc protecting group was followed by the spontaneous cyclative cleavage releasing the 5-methylene-thiohydantoin derivatives from the polymer support. Reduction with triethylsilane (TES) yielded the corresponding 5-methyl-thiohydantoins. When Fmoc-isothiocyanate was replaced with alkyl isothiocyanates, the trifluoroacetic acid (TFA) mediated cleavage from the polymer support, which was followed by the cyclization reaction and the imidazo[2,1-b]thiazol-4-iums were obtained. Their conversion in deuterated dimethylsulfoxide led to imidazole-2-thiones.http://www.mdpi.com/1420-3049/23/4/976heterocyclethiohydantoinimidazoleserinebromoketonesolid-phase synthesis |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Petra Králová Michal Maloň Hiroyuki Koshino Miroslav Soural |
spellingShingle |
Petra Králová Michal Maloň Hiroyuki Koshino Miroslav Soural Convenient Synthesis of Thiohydantoins, Imidazole-2-thiones and Imidazo[2,1-b]thiazol-4-iums from Polymer-Supported α-Acylamino Ketones Molecules heterocycle thiohydantoin imidazole serine bromoketone solid-phase synthesis |
author_facet |
Petra Králová Michal Maloň Hiroyuki Koshino Miroslav Soural |
author_sort |
Petra Králová |
title |
Convenient Synthesis of Thiohydantoins, Imidazole-2-thiones and Imidazo[2,1-b]thiazol-4-iums from Polymer-Supported α-Acylamino Ketones |
title_short |
Convenient Synthesis of Thiohydantoins, Imidazole-2-thiones and Imidazo[2,1-b]thiazol-4-iums from Polymer-Supported α-Acylamino Ketones |
title_full |
Convenient Synthesis of Thiohydantoins, Imidazole-2-thiones and Imidazo[2,1-b]thiazol-4-iums from Polymer-Supported α-Acylamino Ketones |
title_fullStr |
Convenient Synthesis of Thiohydantoins, Imidazole-2-thiones and Imidazo[2,1-b]thiazol-4-iums from Polymer-Supported α-Acylamino Ketones |
title_full_unstemmed |
Convenient Synthesis of Thiohydantoins, Imidazole-2-thiones and Imidazo[2,1-b]thiazol-4-iums from Polymer-Supported α-Acylamino Ketones |
title_sort |
convenient synthesis of thiohydantoins, imidazole-2-thiones and imidazo[2,1-b]thiazol-4-iums from polymer-supported α-acylamino ketones |
publisher |
MDPI AG |
series |
Molecules |
issn |
1420-3049 |
publishDate |
2018-04-01 |
description |
The preparation of 5-methylene-thiohydantoins using solid-phase synthesis is reported in this paper. After sulfonylation of immobilized Ser (t-Bu)-OH with 4-nitrobenzenesulfonyl chloride followed by alkylation with various bromoketones, the 4-Nos group was removed and the resulting polymer-supported α-acylamino ketones reacted with Fmoc-isothiocyanate. Cleavage of the Fmoc protecting group was followed by the spontaneous cyclative cleavage releasing the 5-methylene-thiohydantoin derivatives from the polymer support. Reduction with triethylsilane (TES) yielded the corresponding 5-methyl-thiohydantoins. When Fmoc-isothiocyanate was replaced with alkyl isothiocyanates, the trifluoroacetic acid (TFA) mediated cleavage from the polymer support, which was followed by the cyclization reaction and the imidazo[2,1-b]thiazol-4-iums were obtained. Their conversion in deuterated dimethylsulfoxide led to imidazole-2-thiones. |
topic |
heterocycle thiohydantoin imidazole serine bromoketone solid-phase synthesis |
url |
http://www.mdpi.com/1420-3049/23/4/976 |
work_keys_str_mv |
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