{"created":"2023-07-27T06:44:31.821941+00:00","id":34787,"links":{},"metadata":{"_buckets":{"deposit":"478a9bd0-bfa3-4288-bafc-dd8edd7a12fb"},"_deposit":{"created_by":3,"id":"34787","owners":[3],"pid":{"revision_id":0,"type":"depid","value":"34787"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00034787","sets":["2812:2813:2830"]},"author_link":["93871","155"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2004-03-01","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"12p.","bibliographicVolumeNumber":"2001-2003","bibliographic_titles":[{"bibliographic_title":"平成15(2003)年度科学研究費補助金 基盤研究(B) 研究成果報告書"},{"bibliographic_title":"2003 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":"ラジカル環化反応は環状化合物の新しい有用な合成手段として近年大きな注目を集めており、天然物合成を含む有機合成の領域において現在広く用いられている.しかし,この有用なラジカル環化反応にも解決すべき多くの課題が残されている.その一つは位置化学の制御である.一般に反応を制御しがたいラジカル反応において位置化学の制御の問題が解決されればラジカル反応の有用性はさらに増大するであろう.また,ラジカルの新しい発生法の開発も望まれている.そこで申請者らは,ラジカル環化反応におけるこれらの諸問題の解決を目指すとともに,これらの成果を生理活性化合物の効率的合成法と応用することを目的として本研究を開始し,下記の研究成果知見を得た. 1)硫黄原子によって制御された5-exo選択的アリールラジカルを利用して抗ヘルペスウイルス活性化合物Mappicine Ketoneの新しい合成法を明かにした.2)硫黄原子によって制御された6-exo選択的アリールラジカルを利用して鎮痛作用物質(-)-Aphanorphineの新しい合成法を明らかにした.3)2-位にフェニルチオ基またはフェニル基を有する種々のN-(1-シクロヘキセニル)-α-ハロアミド類のラジカル環化反応における5-endo及び4-exo選択性を明らかにした.4)α-アミドイルラジカルの5-endo型ラジカル環化反応を含む新しいカスケード型ラジカル環化反応を見い出した.5)N-ビニル-α-ハロアミドの5-endo型ラジカル環化反応においてヨウ素原子は脱離基として好ましくないことを明らかにした.6)α-メチルチオアセトアミドをII価の銅塩存在下酢酸マンガン(III)で処理することによりエリスリナン骨格の新しい合成法を見い出し,本反応を天然産エリスリナアルカロイド3-Demethoxyerythratidinoneの合成に応用した.","subitem_description_type":"Abstract"},{"subitem_description":"Radical cyclization was recognized as a valuable tool for the construction of cyclic compounds, and the methods have been widely employed in the field of organic synthesis including natural products synthesis. However, there are many ploblems which required solvation in this useful radical cyclizations. One of them is the controlling regiochemistry. If this problem is solved, the radical cyclization would be highly promising. A new method for generation of radical species is also required. We, therefore, examined several radical cyclizations in more details, and found the following evidences.\n1)A new method for the synthesis of mappicine ketone, an antiherpesvirus compound, has been developed by using sulfur-directed 5-exo selective aryl radical cyclization. 2)A new method for the, synthesis of an analgesic(-)-aphanorphine has been developed by using sulfur-directed 6-exo selective aryl radical cyclization. 3)5-Endo and 4-exo selectivity in radical cyclization of N-(2-phenylthio and 2-phenyl-1-cyclohexenyl)-α-haloamides have been elucidated. 4)A radical cascade involving a 5-endo cyclization of α-amidoyl radicals has been found. 5)It was found that the use of iodine atom as a leaving group is not recommended for the 5-endo radical cyclization of N-vinylic α-haloamides. 6)A new synthesis of erythrinane skeleton which consisted of treatment of α-(methylthio)acetamides with Mn(OAc)_3 in the presence of Cu(II) was found, and the method was applied to the synthesis of 3-demethoxyerythratidinone, a naturally occurring Erythrina alkaloid.","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:13470469, 研究期間(年度):2001–2003","subitem_description_type":"Other"},{"subitem_description":"出典：「新手法に基づくラジカル環化反応を利用する生理活性化合物の合成」研究成果報告書　課題番号13470469\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_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-13470469/","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-13470469/134704692003kenkyu_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 2004-12p.pdf","filesize":[{"value":"504.7 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"PH-PR-ISHIBASHI-H-kaken 2004-12p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/34787/files/PH-PR-ISHIBASHI-H-kaken 2004-12p.pdf"},"version_id":"3aa6a36d-4aaf-415d-9d85-5a3020a5d196"}]},"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":"新手法に基づくラジカル環化反応を利用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":"新手法に基づくラジカル環化反応を利用する生理活性化合物の合成"},{"subitem_title":"Synthesis of Biologically Active Compounds Using Radical Cyclization Based on New Methodologies","subitem_title_language":"en"}]},"item_type_id":"9","owner":"3","path":["2830"],"pubdate":{"attribute_name":"公開日","attribute_value":"2017-10-05"},"publish_date":"2017-10-05","publish_status":"0","recid":"34787","relation_version_is_last":true,"title":["新手法に基づくラジカル環化反応を利用する生理活性化合物の合成"],"weko_creator_id":"3","weko_shared_id":3},"updated":"2023-07-27T14:36:26.554848+00:00"}