{"_buckets": {"deposit": "81565287-fa4c-4db5-a03b-0c4bdd00df89"}, "_deposit": {"created_by": 5, "id": "12825", "owners": [5], "pid": {"revision_id": 0, "type": "depid", "value": "12825"}, "status": "published"}, "_oai": {"id": "oai:gifu-pu.repo.nii.ac.jp:00012825", "sets": ["203"]}, "author_link": ["17854", "17856", "17855"], "item_1_biblio_info_14": {"attribute_name": "書誌情報", "attribute_value_mlt": [{"bibliographicIssueDates": {"bibliographicIssueDate": "2007-06-30", "bibliographicIssueDateType": "Issued"}, "bibliographicPageEnd": "15", "bibliographicPageStart": "1", "bibliographicVolumeNumber": "56", "bibliographic_titles": [{"bibliographic_title": "岐阜藥科大學紀要"}, {"bibliographic_title": "The annual proceedings of Gifu College of Pharmacy", "bibliographic_titleLang": "en"}]}]}, "item_1_creator_6": {"attribute_name": "著者名(日)", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "清水, 洋"}], "nameIdentifiers": [{"nameIdentifier": "17854", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_creator_7": {"attribute_name": "著者名よみ", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "シミズ, ヒロシ"}], "nameIdentifiers": [{"nameIdentifier": "17855", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_creator_8": {"attribute_name": "著者名(英)", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "SHIMIZU, Hiroshi", "creatorNameLang": "en"}], "nameIdentifiers": [{"nameIdentifier": "17856", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_description_1": {"attribute_name": "ページ属性", "attribute_value_mlt": [{"subitem_description": "P(論文)", "subitem_description_type": "Other"}]}, "item_1_description_11": {"attribute_name": "抄録(日)", "attribute_value_mlt": [{"subitem_description": "ヘテロ原子として硫黄を持つ極性活性化学種の付加環化反応の開発と新規ヘテロ環構築への応用を目指し、チオピリリウム塩、1,2-チアジニリウム塩、さらに鎖状のイミノスルホニウム塩の極性付加環化反応を実施した。1-および2-ベンゾチオピリリウム塩、さらに9-チアフェナントレニウム塩などはチエニウムイオン構造(-C=S^+-)を有し、これが電子欠損性の2π系ジエノフィルとして働き、各種の4π電子系の1,3-ジエン類と[2^++4]型極性付加環化反応して多環状のスルホニウム塩形の付加体を高収率で与えることを見出した。また、2-ベンゾチオピリリウム塩においては、電子欠損性の4π系ジエンとしての性質も有し、各種2π電子系多重結合化合物との[4^++2]型極性付加環化反応が進行することを新たに見出した。チオピリリウム塩と等電子構造を有する窒素含有の三環系化合物、ジベンゾ[c,e][1,2]チアジニリウム塩でも-N=S^+-結合部位での[2^++4]型極性付加環化反応の進行がみられ、新規な1,2-チアジン骨格の構築に応用できることを見出した。一方、単環系の1,2-チアジニリウム塩ではチエニウムイオン構造の付加環化反応が優先的に進み、チオピラン誘導体を与えるという興味ある発見をした。この位置特異的反応性をFrontier Molecular Orbitalの軌道係数の比較によって合理的に説明した。さらに、-N=S^+-結合を有する鎖状構造の活性化学種の発生にも成功し、窒素、硫黄上の置換基を変えることによって[2^++4]型と[4^++2]型のいずれかの極性付加環化反応を選択的に進行させることができた。この内、[4^++2]型の反応を発展させてアザチアナフタレンの新規な合成法の発見に結びつけることにも成功した。", "subitem_description_type": "Other"}]}, "item_1_description_12": {"attribute_name": "抄録(英)", "attribute_value_mlt": [{"subitem_description": "Polar cycloadditions of thiopyrylium salts, 1, 2-thiazinylium salts, and acyclic iminosulfonium salts were investigated for the development of cycloaddition of polar active species containing sulfur as a hetero atom and for the application to the construction of novel heterocycles. Thienium ion parts of the 1-benzo- and 2-benzothiopyrylium salts, and 9-thiaphenanthrenium salt underwent [2^++4]-type polar cycloaddition with 1, 3-butadienes to give the corresponding polycyclic sulfonium salts in high yields. 2-Benzothiopyrylium salt was also found to have the reactivity of an electron deficient diene, undergoing [4^++2]-type polar cycloaddition with 2π electron species to give the corresponding cycloadduct. Dibenzo [c, e][1, 2] thiazinylium salt containing a nitrogen atom, having an isoelectronic structure with thiopyrylium salts, underwent [2^++4]-type polar cycloaddition with several 1, 3-butadienes to give the corresponding 1, 2-thiazine derivatives in good yield. On the contrary, monocyclic 1, 2-thiazinylium salts having two types of reactive bonds underwent [2^++4]-type polar cycloaddition with 1, 3-butadiene across the only C=S^+ bond preferentially to form the corresponding thiopyran rings. This complete regiospecificity was rationalized in terms of the Frontier Molecular Orbital coefficients in the salt. Acyclic compounds having a-N=S^+-bond were successfully generated in situ and were found to undergo [2^++4]- or [4^++2]-type polar cycloaddition to afford the corresponding cycloadducts depending on the substituents on the sulfur and nitrogen. The [4^++2]-type polar cycloaddition provided a new synthetic method of azathianaphthalenes.", "subitem_description_type": "Other"}]}, "item_1_source_id_13": {"attribute_name": "雑誌書誌ID", "attribute_value_mlt": [{"subitem_source_identifier": "AN00053514", "subitem_source_identifier_type": "NCID"}]}, "item_1_text_10": {"attribute_name": "著者所属(英)", "attribute_value_mlt": [{"subitem_text_language": "en", "subitem_text_value": "Laboratory of Pharmaceutical English, Gifu Pharmaceutical University"}]}, "item_1_text_2": {"attribute_name": "記事種別(日)", "attribute_value_mlt": [{"subitem_text_value": "総説"}]}, "item_1_text_3": {"attribute_name": "記事種別(英)", "attribute_value_mlt": [{"subitem_text_language": "en", "subitem_text_value": "Review"}]}, "item_1_text_9": {"attribute_name": "著者所属(日)", "attribute_value_mlt": [{"subitem_text_value": "岐阜薬科大学薬学英語研究室"}]}, "item_files": {"attribute_name": "ファイル情報", "attribute_type": "file", "attribute_value_mlt": [{"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2007-06-30"}], "displaytype": "detail", "download_preview_message": "", "file_order": 0, "filename": "KJ00004767745.pdf", "filesize": [{"value": "1.3 MB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_free", "mimetype": "application/pdf", "size": 1300000.0, "url": {"url": "https://gifu-pu.repo.nii.ac.jp/record/12825/files/KJ00004767745.pdf"}, "version_id": "58832776-d0c9-4b96-aa16-4d546a2d8f2f"}]}, "item_keyword": {"attribute_name": "キーワード", "attribute_value_mlt": [{"subitem_subject": "チオピリリウム塩", "subitem_subject_scheme": "Other"}, {"subitem_subject": "1,2-チアジニリウム塩", "subitem_subject_scheme": "Other"}, {"subitem_subject": "[2^++4]型極性付加環化反応", "subitem_subject_scheme": "Other"}, {"subitem_subject": "[4^++2]型極性付加環化反応", "subitem_subject_scheme": "Other"}, {"subitem_subject": "1,3-ブタジエン", "subitem_subject_scheme": "Other"}, {"subitem_subject": "電子欠損性ジエン", "subitem_subject_scheme": "Other"}, {"subitem_subject": "thiopyrylium salt", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}, {"subitem_subject": "1, 2-thiazinylium salt", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}, {"subitem_subject": "[2^++4] polar cycloaddition", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}, {"subitem_subject": "[4^++2] polar cycloaddition", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}, {"subitem_subject": "1, 3-butadiene", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}, {"subitem_subject": "electron deficient diene", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}]}, "item_language": {"attribute_name": "言語", "attribute_value_mlt": [{"subitem_language": "jpn"}]}, "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": "チオピリリウム塩および関連硫黄化合物の極性付加環化反応の開発と新規ヘテロ環構築への応用", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "チオピリリウム塩および関連硫黄化合物の極性付加環化反応の開発と新規ヘテロ環構築への応用"}, {"subitem_title": "Development of Polar Cycloaddition of Thiopyrylium Salts and Related Sulfur Compounds and Application to the Construction of Novel Heterocyles", "subitem_title_language": "en"}]}, "item_type_id": "1", "owner": "5", "path": ["203"], "permalink_uri": "https://gifu-pu.repo.nii.ac.jp/records/12825", "pubdate": {"attribute_name": "公開日", "attribute_value": "2007-06-30"}, "publish_date": "2007-06-30", "publish_status": "0", "recid": "12825", "relation": {}, "relation_version_is_last": true, "title": ["チオピリリウム塩および関連硫黄化合物の極性付加環化反応の開発と新規ヘテロ環構築への応用"], "weko_shared_id": -1}