{"created":"2023-07-27T06:56:32.313386+00:00","id":53370,"links":{},"metadata":{"_buckets":{"deposit":"4b8046f0-290e-436e-8446-fb5f00bacc01"},"_deposit":{"created_by":18,"id":"53370","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"53370"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00053370","sets":["2812:2813:2830"]},"author_link":["148"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2005-04-18","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"2p.","bibliographicVolumeNumber":"2002 – 2003","bibliographic_titles":[{"bibliographic_title":"平成15(2003)年度 科学研究費補助金 基盤研究(C) 研究成果報告書概要"},{"bibliographic_title":"2003 Fiscal Year Final Research Report Summary","bibliographic_titleLang":"en"}]}]},"item_9_creator_33":{"attribute_name":"著者別表示","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{}],"nameIdentifiers":[{},{},{},{}]}]},"item_9_description_21":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"アレン類は3個の連続した炭素から成り,C-1及びC-3位がsp2混成軌道を,C-2炭素が集積されたsp混成軌道を持つ,他の化合物とは際立って異なった構造的特色を有している.著者はそのハイブリッド混成ユニットに着目した.そこで,C-1位に電子吸引性基を内蔵すると共にC-1位にδ-酸素或いは窒素官能基含有側鎖を併せ持つ,1,1-disubstitutedアレン類を合成し弱塩基処理すれば,C-2集積炭素上でMichael型分子内閉環反応,言い換えれば,エンド型分子内共役付加環化反応(Baldwin則に従うならばendo-dig型反応)が進行し,対応するヘテロ環化合物が効率よく得られるものと考えた.Baldwin則を基に推考すれば,5員環,6員環の通常環ヘテロ環化合物構築は言うに及ばず,中員環ヘテロ環化合物合成への応用も高い確立で達成できるものと考えた.\n以上の考えに基づき,1位にフェニルスルフィニル基とδ-酸素官能基含有アルキル側鎖を併せ持つ,1,1-disubstitutedアレン類を対応するプロパルギルアルコール誘導体から合成し,^tBuOKを塩基としてエンド型閉環反応を行った.その結果,速やかに反応は進行し,5〜7員環含酸素ヘテロ環が高収率で得られることを見出した.しかし,中員環の8員環形成は進行しなかった.そこで,1位フェニルスルフィニル基の代わりに,より酸化度の進んだフェニルスルホニル基を1位に導入して,同様の閉環反応を行ったところ,目的の含酸素8員環化合物を良好な収率で合成することに成功した.\nδ-酸素官能基含有アルキル側鎖の代わりに,δ-窒素官能基含有アルキル側鎖を用いて同様のエンド型閉環反応を検討し,対応する含窒素ヘテロ環化合物の合成法の開発にも成功した.更に,δ位に活性メチン基をもつアレンのエンド型閉環反応も試み,対応する炭素環構築にもアレンのエンド型閉環反応が適用可能であることを明らかとした.","subitem_description_type":"Abstract"},{"subitem_description":"The base-catalyzed the endo mode ring-closing reaction of 1-allenyl sulfoxides having a suitable alkyl side chain with the4erininal oxygen atom proceed as to afford the corresponding 5〜7-menibered oxacycles.Changing the sulfinyl group of the allenes to ths sulfonyl group brought some improvement resulting in the formation of 5〜8-membered oxacycles.This novel endo mode ring-closing reaction of allenes was applied to the congeners possessing the terminal nitrogen functionality and active methane group to give the corresppnding cyclized products in acceptable yields.Thus, this method was demonstrated to be applicable to various kinds of allenes.","subitem_description_type":"Abstract"}]},"item_9_description_22":{"attribute_name":"内容記述","attribute_value_mlt":[{"subitem_description":"研究課題/領域番号:14571998, 研究期間(年度):2002 – 2003","subitem_description_type":"Other"},{"subitem_description":"出典：研究課題「エンド型閉環反応を基盤とする効率的ヘテロ中員環構築法の開発」課題番号14571998\n（KAKEN：科学研究費助成事業データベース（国立情報学研究所）） \n（https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-14571998/145719982003kenkyu_seika_hokoku_gaiyo/）を加工して作成","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00059653","subitem_identifier_reg_type":"JaLC"}]},"item_9_relation_28":{"attribute_name":"関連URI","attribute_value_mlt":[{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/search/?kw=70143914"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/search/?kw=70143914","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-14571998/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-14571998/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-14571998/145719982003kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-14571998/145719982003kenkyu_seika_hokoku_gaiyo/","subitem_relation_type_select":"URI"}}]},"item_9_version_type_25":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_ab4af688f83e57aa","subitem_version_type":"AM"}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2022-05-19"}],"displaytype":"detail","filename":"PH-PR-MUKAI-C-kaken 2005-2p.pdf","filesize":[{"value":"81.0 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"PH-PR-MUKAI-C-kaken 2005-2p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/53370/files/PH-PR-MUKAI-C-kaken 2005-2p.pdf"},"version_id":"25afade1-91c1-413e-b722-7edbfeced331"}]},"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":"research report","resourceuri":"http://purl.org/coar/resource_type/c_18ws"}]},"item_title":"エンド型閉環反応を基盤とする効率的ヘテロ中員環構築法の開発","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"エンド型閉環反応を基盤とする効率的ヘテロ中員環構築法の開発"},{"subitem_title":"Development of efficient method for construction of medium-sized heterocycles based on endo mode cyclization","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2830"],"pubdate":{"attribute_name":"公開日","attribute_value":"2022-05-19"},"publish_date":"2022-05-19","publish_status":"0","recid":"53370","relation_version_is_last":true,"title":["エンド型閉環反応を基盤とする効率的ヘテロ中員環構築法の開発"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T13:05:40.911328+00:00"}