{"created":"2023-07-27T06:56:32.358190+00:00","id":53371,"links":{},"metadata":{"_buckets":{"deposit":"baaab5a7-c1e8-40b2-b5ec-bb3a14bd9c87"},"_deposit":{"created_by":18,"id":"53371","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"53371"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00053371","sets":["2812:2813:2827"]},"author_link":["148"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2008-05-26","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"3p.","bibliographicVolumeNumber":"2004 – 2006","bibliographic_titles":[{"bibliographic_title":"平成18(2006)年度 科学研究費補助金 基盤研究(B) 研究成果報告書概要"},{"bibliographic_title":"2006 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":"申請者はアレンの特性を活用した新規反応の開発を目途に,1位に電子吸引性置換基(例えばフェニルスルホニル基)を有する基質を用いて検討を重ねた結果,以下の新規反応の開発に成功した.1.アルキル側鎖上の適当な位置に水酸基(或はアミノ基,カルバニオン等)を有する1-アルキル置換-1-スルホニルアレンを塩基で処理すると,新規なエンド型閉環反応(sp混成炭素への求核攻撃)が選択的に進行し,5〜9員環化合物が良好な収率で得られることを明らかにした.なお,電子吸引性基として,スルホニル基の代わりにスルホキシド基,ホスフィンオキシド基,ホスホナート基,エステル等を適宜選択しても,上記エンド型反応を進行させることが可能である.加えて,オルト位にアレニル基を有するアニリン誘導体を出発原料にして2,3-ジ置換インドール骨格の新規合成法やインドール-2,3-キノジメタンの発生法も確立した.2.アレンーアルキンのロジウム触媒を活用する分子内Pauson-Khand型反応を検討し,通常のエンイン体では合成困難なbicyco[5.3.0]骨格を容易に合成できることを見出した.また,アレンーアルケン体を用いても同様の反応が進行することが明らかとなった.さらに,アレンの代わりにカルボジイミドを用いた触媒的ヘテロPauson-Khand反応の開発にも成功した.3.二つのアレン部をベンゼン環或はオレフィンで連結させたビスアレン誘導体を発生させると,速やかに6π-電子環状反応を起こし,対応する2,3-キノジメタン誘導体が得られることを見出した.本反応において,反応系、内にジエノフィルが存在すると,2,3-キノジメタン誘導体とのDiels-Alder型反応が容易に進行することも確認した.本反応を応用して,鎖状化合物からステロイド骨格を一挙に構築する手法を確立した.また,本反応のアレン生成過程において,条件を適宜選択すると,2,3-キノジメタン誘導体から対応するシクロブテン誘導体を合成することも可能である.","subitem_description_type":"Abstract"},{"subitem_description":"This program has been directed toward development of efficient and novel reactions based on the inherent property of allenes, in particular, the allene possessing an electron-withdrawing group such as a phenylsulfonyl group. As a result, the following several reactions could be developed.\n(1) Treatment of 1-phenylsulfonylallene with a proper (co-hydroxy) alkyl side chain at the C,-position with a base afforded the corresponding oxacycles through the endo-mode cyclization process. This novel ring-closing reaction could be applied for the construction of five-to nine-membered oxacycles. The aza-congeners as well as carbocycles were also found to be prepared according to the standard conditions, thus developed. The sulfoxide, phosphine oxide, phosphonate, and ester functionalities were used as an electron-withdrawing group instead a sulfonyl moiety. Furthermore, allenylaniline derivatives provided the corresponding 2,3-disubstituted indoles in an endo-mode ring-closing manner. The allenyla niline having a hydroxymethyl group was converted into the indole-2,3-quinodimethane derivative via the intramolecular SN2' reaction.\n(2) The Pauson-Khand reaction of allenynes in the presence of Rh catalyst resulted in the efficient formation of bicyclo[4.3.0] as well as bicyclo[5.3.0] skeletons, the latter of which could not be prepared by the Pauson-Khand reaction of enynes. This new-type of Pauson-Khand reaction furnished the bicyclo[6.3.0] framswork as well. Alternatively, the carbodlimide functionality, which is isoelectronic to the allene group, could be successfully used in the Pauson-Khand reaction leading to the efficient construction of pyrrolo[2,3-b]indo1-2-ones.\n(3) Reaction of ene-bisallenes, generated from the corresponding propargyl alcohols, underwent the 6π-electrocyclic reaction to afford the quinodimethanes, which were susceptible to the [4+2]cycloaddition reaction with dienophiles. This novel method for the generation of quinodimethane species could be applied for the production of the naphthoquinodimethanes from benzene-bridged bisallene. Interestingly enough, the proper choice of the conditions in the step of bis-allene formation produced the cyclobutene derivatives instead of the [4+2]cycloadducts even if the suitable dienophiles were in existence.","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:16390005, 研究期間(年度):2004 – 2006","subitem_description_type":"Other"},{"subitem_description":"出典：研究課題「アレン化学の新展開」課題番号16390005\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-16390005/163900052006kenkyu_seika_hokoku_gaiyo/）を加工して作成","subitem_description_type":"Other"}]},"item_9_description_5":{"attribute_name":"提供者所属","attribute_value_mlt":[{"subitem_description":"金沢大学医薬保健研究域薬学系","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00059654","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-16390005/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-16390005/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-16390005/163900052006kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-16390005/163900052006kenkyu_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 2008-3p.pdf","filesize":[{"value":"115.9 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"PH-PR-MUKAI-C-kaken 2008-3p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/53371/files/PH-PR-MUKAI-C-kaken 2008-3p.pdf"},"version_id":"168662b7-6a4c-40ec-b44d-48ea49a4ec28"}]},"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":"アレン化学の新展開","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"アレン化学の新展開"},{"subitem_title":"New Aspect on the Chemistry of Allenes","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2827"],"pubdate":{"attribute_name":"公開日","attribute_value":"2022-05-19"},"publish_date":"2022-05-19","publish_status":"0","recid":"53371","relation_version_is_last":true,"title":["アレン化学の新展開"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T13:06:10.341845+00:00"}