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The 1, 3-dipolar cycloaddition reaction is one of the most important reaction to construct five-membered heterocycles. We have reported that tailor-made azomethine and thiocarbonyl ylids can be generated by the 1, 3-elimionation reaction of trimethylsilylmethyl- substituted ketene N,S- or S,S- acetals promoted by fluoride ion and react with dipolarophiles to give five-membered heterocycles. As an unpublished result, we have recognized that the reactuion of 3-trimethylsilylmethylamino-3-methylthio-2- cyanoacrylonitrile with dipolarophiles in the presence of a fluoride ion gives five-membered heterocycles but the reaction of 3-trimethylsilylmethylamino-2-cyanoacrylonitrile with dipolarophiles gives no cycloadducts. These facts have shown that the elimination of a methylthio group following cleavage of carbon-silicon bond is a useful tool for the generation of 1,3-dipolar. Here we descrive the reaction of N-(trimethylsilylmethyl)-2- methythiothiazolinium trifluoromethanesulfonate, which has a Me3SiCH2 -N=C-SMe system, with dipolarophiles gives 4,5-dihydropyrrolo [2,1 - b] thiazoline derivatives. Trimethysilylmethyl trifluoromethanesulfonate (1) is an interesting compound to the preparation of silicon-containing sulfonium, nitrogen and other ylids. Starting material 1 was prepared according to the literature. A solution of 2-methylthiothiazoline (2) in dichloromethane was treated with 1 and stirred at room temperature for over night. After the solvent was removed N- (trimethylsilymethyl)-2-methylthiothiazolinium trifluoromethanesulfonate (4) was afforded. The crude salt 4 was used in the next step without purification. A solution of 4, thus obtained, and dimethyl fumarate(6b) in the prsence of cesium fluoride in acetonitrile was stirred at room temperature for 24h. The usual work-up after treatment with aqueous ammonium chloride and separation by preparative t.l.c. gave dimethyl 4,5-dihydropyrrolo [2, 1-b] thiazoline -5, 6-dicarboxylate(7b), formal [3+2] cycloaddition product, in 53% yield. The cycloadditon behavior of an unsymmetrically substituted dipolarophile was studied to determine the regioselectivity of the reaction. The reaction of 4 and methyl acrylate (6a) under the similar conditions gave methyl 4,5-dihydop yrrolo [2,1-b] thiazoline-6-carboxylate (7a) in 57% yield, exclusively. When methyl cinnamate (6d) was used as a dipolarophile, cycloadduct 7d was obtained as a single pro duct. The representative results are listed in Table 1. N-(Trimethylsilylmethyl)-2- methylthiobenzothia-zolium trifluoromethenesulfonate (5) was also prepared and reacted with activated alkenes (6a-6d) to give the corresponding [3+2] cycloadducts (8a-8d) in a manner similar to that described for 7a. The reaction also shows complete regiospecificity in the cycloaddition with unsymmetrically substituted olefins. However the reactions of 4 and 5 with N-methylmaleimide was unsuccessful under the present reaction conditions. Salt 4 and 5 reacted with alkynes (9a and 9b) under the similar conditions to give [3+2] cycloaiddition products, pyrrolo [2, 1-b] thiazoline derivatives(10a and 10b) and pyrrolo [2, 1-b] benzothiazole derivatives (11a and 11b). (see Table 2) This work demonstrates a mild and simple procedure for the preparation of pyrrolo [2, 1-b] thiazoline and pyrrolo [2, 1-b] benzothiazole derivatives.", "subitem_description_type": "Abstract"}]}, "item_3_description_64": {"attribute_name": "引用", "attribute_value_mlt": [{"subitem_description": "長崎大学教養部紀要. 自然科学篇. 1996, 37(2), p.13-20", "subitem_description_type": "Other"}]}, "item_3_full_name_3": {"attribute_name": "著者別名", "attribute_value_mlt": [{"nameIdentifiers": [{"nameIdentifier": "87321", "nameIdentifierScheme": "WEKO"}], "names": [{"name": "高良, 真也"}]}, {"nameIdentifiers": [{"nameIdentifier": "87322", "nameIdentifierScheme": "WEKO"}], "names": [{"name": "上江田, 一雄"}]}]}, "item_3_source_id_10": {"attribute_name": "書誌レコードID", "attribute_value_mlt": [{"subitem_source_identifier": "AN10352293", "subitem_source_identifier_type": "NCID"}]}, "item_3_source_id_7": {"attribute_name": "ISSN", "attribute_value_mlt": [{"subitem_source_identifier": "02871319", "subitem_source_identifier_type": "ISSN"}]}, "item_3_text_62": {"attribute_name": "sortkey", "attribute_value_mlt": [{"subitem_text_value": "P00013-P00020"}]}, "item_3_version_type_16": {"attribute_name": "著者版フラグ", "attribute_value_mlt": [{"subitem_version_resource": "http://purl.org/coar/version/c_970fb48d4fbd8a85", "subitem_version_type": "VoR"}]}, "item_creator": {"attribute_name": "著者", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "Kohra, Shinya"}], "nameIdentifiers": [{"nameIdentifier": "87319", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Ueda, Kazuo"}], "nameIdentifiers": [{"nameIdentifier": "87320", "nameIdentifierScheme": "WEKO"}]}]}, "item_files": {"attribute_name": "ファイル情報", "attribute_type": "file", "attribute_value_mlt": [{"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2020-12-23"}], "displaytype": "detail", "download_preview_message": "", "file_order": 0, "filename": "kyoyoS37_02_02_t.pdf", "filesize": [{"value": "400.6 kB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_free", "mimetype": "application/pdf", "size": 400600.0, "url": {"label": "kyoyoS37_02_02_t.pdf", "url": "https://nagasaki-u.repo.nii.ac.jp/record/20705/files/kyoyoS37_02_02_t.pdf"}, "version_id": "790836cd-97bf-4473-869e-712574ae2a1f"}]}, "item_language": {"attribute_name": "言語", "attribute_value_mlt": [{"subitem_language": "eng"}]}, "item_resource_type": {"attribute_name": "資源タイプ", "attribute_value_mlt": [{"resourcetype": "departmental bulletin paper", "resourceuri": "http://purl.org/coar/resource_type/c_6501"}]}, "item_title": "Synthesis of Pyrrolo [2,1-b] thiazolines Using N-(Trimethylsilylmethyl)-2- methylthiothiazolinium Trifluoromethanesulfonate", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "Synthesis of Pyrrolo [2,1-b] thiazolines Using N-(Trimethylsilylmethyl)-2- methylthiothiazolinium Trifluoromethanesulfonate"}]}, "item_type_id": "3", "owner": "2", "path": ["1462"], "permalink_uri": "http://hdl.handle.net/10069/16662", "pubdate": {"attribute_name": "公開日", "attribute_value": "2008-04-14"}, "publish_date": "2008-04-14", "publish_status": "0", "recid": "20705", "relation": {}, "relation_version_is_last": true, "title": ["Synthesis of Pyrrolo [2,1-b] thiazolines Using N-(Trimethylsilylmethyl)-2- methylthiothiazolinium Trifluoromethanesulfonate"], "weko_shared_id": -1}
Synthesis of Pyrrolo [2,1-b] thiazolines Using N-(Trimethylsilylmethyl)-2- methylthiothiazolinium Trifluoromethanesulfonate
http://hdl.handle.net/10069/16662
http://hdl.handle.net/10069/1666233b3bda8-a9f3-4773-b604-329f927f65a4
名前 / ファイル | ライセンス | アクション |
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kyoyoS37_02_02_t.pdf (400.6 kB)
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Item type | 紀要論文 / Departmental Bulletin Paper(1) | |||||
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公開日 | 2008-04-14 | |||||
タイトル | ||||||
タイトル | Synthesis of Pyrrolo [2,1-b] thiazolines Using N-(Trimethylsilylmethyl)-2- methylthiothiazolinium Trifluoromethanesulfonate | |||||
言語 | ||||||
言語 | eng | |||||
資源タイプ | ||||||
資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
資源タイプ | departmental bulletin paper | |||||
著者 |
Kohra, Shinya
× Kohra, Shinya× Ueda, Kazuo |
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著者別名 | ||||||
姓名 | 高良, 真也 | |||||
著者別名 | ||||||
姓名 | 上江田, 一雄 | |||||
抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | N-(Trimethylsilylmethyl)-2-methylthiothiazolinium trifluoromethanesulfonate(4), readily prepard from 2-methylthiothiazoline (2) and trimethylsilylmethyl trifluoromethenesulfonate (1), reacted with activated alkenes (5) and alkynes (6) in the presence of cesium fluoride in acetonitrile to give the corresponding 4, 5-dihydropyrrolo [2, 1-b] thiazoline and pyrrolo [2, 1-b] thiazoline derivatives. The 1, 3-dipolar cycloaddition reaction is one of the most important reaction to construct five-membered heterocycles. We have reported that tailor-made azomethine and thiocarbonyl ylids can be generated by the 1, 3-elimionation reaction of trimethylsilylmethyl- substituted ketene N,S- or S,S- acetals promoted by fluoride ion and react with dipolarophiles to give five-membered heterocycles. As an unpublished result, we have recognized that the reactuion of 3-trimethylsilylmethylamino-3-methylthio-2- cyanoacrylonitrile with dipolarophiles in the presence of a fluoride ion gives five-membered heterocycles but the reaction of 3-trimethylsilylmethylamino-2-cyanoacrylonitrile with dipolarophiles gives no cycloadducts. These facts have shown that the elimination of a methylthio group following cleavage of carbon-silicon bond is a useful tool for the generation of 1,3-dipolar. Here we descrive the reaction of N-(trimethylsilylmethyl)-2- methythiothiazolinium trifluoromethanesulfonate, which has a Me3SiCH2 -N=C-SMe system, with dipolarophiles gives 4,5-dihydropyrrolo [2,1 - b] thiazoline derivatives. Trimethysilylmethyl trifluoromethanesulfonate (1) is an interesting compound to the preparation of silicon-containing sulfonium, nitrogen and other ylids. Starting material 1 was prepared according to the literature. A solution of 2-methylthiothiazoline (2) in dichloromethane was treated with 1 and stirred at room temperature for over night. After the solvent was removed N- (trimethylsilymethyl)-2-methylthiothiazolinium trifluoromethanesulfonate (4) was afforded. The crude salt 4 was used in the next step without purification. A solution of 4, thus obtained, and dimethyl fumarate(6b) in the prsence of cesium fluoride in acetonitrile was stirred at room temperature for 24h. The usual work-up after treatment with aqueous ammonium chloride and separation by preparative t.l.c. gave dimethyl 4,5-dihydropyrrolo [2, 1-b] thiazoline -5, 6-dicarboxylate(7b), formal [3+2] cycloaddition product, in 53% yield. The cycloadditon behavior of an unsymmetrically substituted dipolarophile was studied to determine the regioselectivity of the reaction. The reaction of 4 and methyl acrylate (6a) under the similar conditions gave methyl 4,5-dihydop yrrolo [2,1-b] thiazoline-6-carboxylate (7a) in 57% yield, exclusively. When methyl cinnamate (6d) was used as a dipolarophile, cycloadduct 7d was obtained as a single pro duct. The representative results are listed in Table 1. N-(Trimethylsilylmethyl)-2- methylthiobenzothia-zolium trifluoromethenesulfonate (5) was also prepared and reacted with activated alkenes (6a-6d) to give the corresponding [3+2] cycloadducts (8a-8d) in a manner similar to that described for 7a. The reaction also shows complete regiospecificity in the cycloaddition with unsymmetrically substituted olefins. However the reactions of 4 and 5 with N-methylmaleimide was unsuccessful under the present reaction conditions. Salt 4 and 5 reacted with alkynes (9a and 9b) under the similar conditions to give [3+2] cycloaiddition products, pyrrolo [2, 1-b] thiazoline derivatives(10a and 10b) and pyrrolo [2, 1-b] benzothiazole derivatives (11a and 11b). (see Table 2) This work demonstrates a mild and simple procedure for the preparation of pyrrolo [2, 1-b] thiazoline and pyrrolo [2, 1-b] benzothiazole derivatives. | |||||
書誌情報 |
長崎大学教養部紀要. 自然科学篇 巻 37, 号 2, p. 13-20, 発行日 1996-10-31 |
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ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 02871319 | |||||
書誌レコードID | ||||||
収録物識別子タイプ | NCID | |||||
収録物識別子 | AN10352293 | |||||
著者版フラグ | ||||||
出版タイプ | VoR | |||||
出版タイプResource | http://purl.org/coar/version/c_970fb48d4fbd8a85 | |||||
sortkey | ||||||
P00013-P00020 | ||||||
引用 | ||||||
内容記述タイプ | Other | |||||
内容記述 | 長崎大学教養部紀要. 自然科学篇. 1996, 37(2), p.13-20 |