{"created":"2023-05-15T16:44:52.919381+00:00","id":20705,"links":{},"metadata":{"_buckets":{"deposit":"04a0b826-cd1e-4ca3-97f9-05e62e540195"},"_deposit":{"created_by":2,"id":"20705","owners":[2],"pid":{"revision_id":0,"type":"depid","value":"20705"},"status":"published"},"_oai":{"id":"oai:nagasaki-u.repo.nii.ac.jp:00020705","sets":["1273:1274:1275:1462"]},"author_link":["87320","87321","87319","87322"],"item_3_biblio_info_6":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1996-10-31","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"2","bibliographicPageEnd":"20","bibliographicPageStart":"13","bibliographicVolumeNumber":"37","bibliographic_titles":[{"bibliographic_title":"長崎大学教養部紀要. 自然科学篇"}]}]},"item_3_description_4":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"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 As an unpublished result, we have recognized that the reactuion of 3-trimethylsilylmethylamino-3-methylthio-2- cyanoacrylonitrile with dipolarophiles in the presence of a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.","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":[{}]},{"creatorNames":[{"creatorName":"Ueda, Kazuo"}],"nameIdentifiers":[{}]}]},"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","filename":"kyoyoS37_02_02_t.pdf","filesize":[{"value":"400.6 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","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"],"pubdate":{"attribute_name":"公開日","attribute_value":"2008-04-14"},"publish_date":"2008-04-14","publish_status":"0","recid":"20705","relation_version_is_last":true,"title":["Synthesis of Pyrrolo [2,1-b] thiazolines Using N-(Trimethylsilylmethyl)-2- methylthiothiazolinium Trifluoromethanesulfonate"],"weko_creator_id":"2","weko_shared_id":-1},"updated":"2023-05-16T02:24:36.273956+00:00"}