{"created":"2023-07-27T06:44:33.694704+00:00","id":34830,"links":{},"metadata":{"_buckets":{"deposit":"f2ab792d-7ec7-420e-a8bc-bc4ee79a60e3"},"_deposit":{"created_by":3,"id":"34830","owners":[3],"pid":{"revision_id":0,"type":"depid","value":"34830"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00034830","sets":["2812:2813:2833"]},"author_link":["93871","155"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2001-03-01","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"13p.","bibliographicVolumeNumber":"1999-2000","bibliographic_titles":[{"bibliographic_title":"平成12(2000)年度 科学研究費補助金 基盤研究(C) 研究成果報告書"},{"bibliographic_title":"2000 Fiscal Year Final Research Report","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":"1.アルケンに対するラジカル環化反応において,アルケン末端に硫黄原子やシアノ基を導入すると,環化反応がexo型でのみ効率良く進行することを見出した.また,これらの結果に対する機構的考察を行うと共に,本反応を(±)-イパルビジン及び(±)-フイゾスチグミンの重要中間体の合成に応用した. 2.5-exo型ラジカル環化反応を用いる(3R^*,3aS^*,7aS^*)-3-アリールオクタヒドロインドール-2-オン類の立体選択的合成法を見出し,本反応を(±)-パンクラシンの形式合成に応用した. 3.N-ビニル2-ヨードベンズアミドのラジカル環化反応の位置化学について検討し,6-endo環化体はアリールラジカルの5-exo環化と引き続くネオフィル転位を経て生成していることを明らかにした. 4.N-(o-ブロモベンジル)エナミドのアリールラジカル環化反応について検討し,オレフィン上に置換基を持たない化合物のラジカル環化反応が6-endo環化体のみを与えるという初めての例を見出し,また,オレフィン末端に2つの硫黄原子を導入すると5-exo環化体のみが得られることも明らかにした.さらに,5-exo選択的アリールラジカル環化反応を抗ヘルペスウイルス活性物質マッピシンケトンのモデル化合物の合成に応用した. 5.ハロゲン化合物のラジカル反応においてはクロロ原子よりもヨウ素原子を用いる方が良い結果を与えることが知られている.ところが,α-ハロアミドの5-endo型ラジカル環化反応においては,クロロ原子を用いると好収率で環化体を与えるが,ヨウ素原子を用いると環化体がほとんど得られない,という興味深い結果を与えた. 6.酢酸マンガン(III)-酢酸銅(II)系を用いるα-メチルチオアミドの酸化的ラジカル環化反応を見出し,本反応をエリスリナン骨格の短工程合成法を応用した.","subitem_description_type":"Abstract"},{"subitem_description":"1. Radical cyclization of ω-haloalkenes having a sulfur atom or a nitrile group at the terminus of their alkenic bond was found to undergo in an exo manner exclusively. A mechanistic rationalization for the results was proposed and the methods were applied to the syntheses of the key intermediates for (±)-ipalbidine and (±)-physostigmine.\n2. Stereoselective synthesis of (3R^*, 3aS^*, 7aS^*)-3-aryloctahydroindol-2-ones using 5-exo radical cyclization was developed and the method was applied to a formal synthesis of (±)-pancracine.\n3. Formation of 6-endo cyclization products by radical reaction of N-vinylic 2-iodobenzamides was found to proceed through a consecutive 5-exo aryl radical cyclization and neophyl rearrangement.\n4. In the course of the study on the radical cyclization of N-(ο-bromobenzyl) enamides, we found a first example of the formation of 6-endo cyclization product onto alkene having no substituent on the alkenic bond. We also found that the enamides having two phenylthio groups at the terminus or the N-vinylic bond underwent radical cyclization in a 5-exo manner exclusively. The latter method was applied to the synthesis of a model compound of mappicine ketone, an anti-herpesvirus compound.\n5. The use of an iodine atom is recognized to give a better result than does that of a chlorine atom in the radical reactions of halogeno compounds. We found, surprisingly, that in the 5-endo cyclization of α-halo amides, the use of a chlorine atom gave the cyclization products in high yields, whereas that of an iodine atom gave only a limited amount of the expected cyclization product.\n6. Mu(OAc)_3/Cu(OAc)_2-mediated oxidative radical cyclization of α-(methylthio) amides was developed and the method was applied to a concise construction of an erythrinane skeleton.","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:11672099, 研究期間(年度):1999–2000","subitem_description_type":"Other"},{"subitem_description":"出典：「位置及び立体制御ラジカル環化反応を基盤とする生理活性化合物の合成」研究成果報告書　課題番号11672099\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　　　本文データは著者版報告書より作成","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00034817","subitem_identifier_reg_type":"JaLC"}]},"item_9_publisher_17":{"attribute_name":"公開者","attribute_value_mlt":[{"subitem_publisher":"金沢大学薬学部"}]},"item_9_relation_28":{"attribute_name":"関連URI","attribute_value_mlt":[{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/search/?qm=70028869","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11672099/","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-11672099/116720992000kenkyu_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":"2017-10-05"}],"displaytype":"detail","filename":"PH-PR-ISHIBASHI-H-kaken 2001-13p.pdf","filesize":[{"value":"293.4 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"PH-PR-ISHIBASHI-H-kaken 2001-13p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/34830/files/PH-PR-ISHIBASHI-H-kaken 2001-13p.pdf"},"version_id":"c577fbc3-85fa-48e0-a9b8-cdc33e2310ca"}]},"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":"位置及び立体制御ラジカル環化反応を基盤とする生理活性化合物の合成","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"位置及び立体制御ラジカル環化反応を基盤とする生理活性化合物の合成"},{"subitem_title":"Synthesis of Biologically Active Compounds Based on the Regio- and Stereo-Controlled Radical Cyclizations","subitem_title_language":"en"}]},"item_type_id":"9","owner":"3","path":["2833"],"pubdate":{"attribute_name":"公開日","attribute_value":"2017-10-05"},"publish_date":"2017-10-05","publish_status":"0","recid":"34830","relation_version_is_last":true,"title":["位置及び立体制御ラジカル環化反応を基盤とする生理活性化合物の合成"],"weko_creator_id":"3","weko_shared_id":3},"updated":"2023-07-27T14:46:09.199628+00:00"}