{"created":"2023-07-27T07:00:06.407976+00:00","id":59917,"links":{},"metadata":{"_buckets":{"deposit":"0c12838e-d4b6-4f17-ae97-172049722780"},"_deposit":{"created_by":18,"id":"59917","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"59917"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00059917","sets":["2812:2813:2836"]},"author_link":["155"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1999-03-15","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"3p.","bibliographicVolumeNumber":"1996 – 1997","bibliographic_titles":[{"bibliographic_title":"平成9(1997)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":"1997 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":"ラジカル環化反応における位置および立体化学の制御に関して研究を行い、以下の知見を得た。\n1.ビニル基末端にチオ基またはフェニル基を有するN-ビニル-α-ブロモアミドの4-exo選択的ラジカル環化反応の不斉誘起を検討し、高い不斉収率でβ-ラクタムが得られることを見いだした。また、本反応をカルバペネム系抗生物質(+)-PS-5、(+)-チエナマイシンおよび1β-メチルカルバペネムの新しい合成法に応用した。\n2.窒素原子上に光学活性な1-フェニルエチル基を有するN-(1-シクロアルケン-1-イル)-αブロモアミドの5-endo選択的ラジカル環化反応においても良好な不斉誘起が起こることを明らかにし、本反応を(-)-γ-リコランの合成に応用した。\n3.オレフィン末端にフェニルチオ基を有するN-(1-シクロヘキセン-1-イル)-α-ハロアミドのラジカル環化反応を検討したところ、速度論的支配条件下では4-exo型に、熱力学的支配条件下では5-endo型にそれぞれ環化反応が進行することを明らかにした。\n4.ビニル基末端にチオ基を有するN-ビニル-2-ブロモベンズアミドおよびN-ビニル-2-(2-ブロモフェニル)アセトアミドがそれぞれ効率良く5-exoおよび6-exo型アリールラジカル環化反応を行うことを見いだし、本反応をチレニン、レンノキサミン、テトラヒドロパルマチンおよびソ-ラチン等アルカロイドの合成に応用した。\n5.N-[0-(2-プロペニル)フェニル]-2,2-ビス(フェニルチオ)アセトアミドが位置選択的に8-endo型ラジカル環化反応を行うことを見いだした。","subitem_description_type":"Abstract"},{"subitem_description":"Bu_3SnH-mediated regio- and stereoselective radical cyclizations of alpha-holo amides have been examined. The results are summarized below.\n1. The 4-exo radical cyclization of N-vinylic alpha-halo amides, bearing a chiral auxiliary on the nitrogen atom or at the alpha-position of the carbonyl group, was found to proceed with high degree of diastereoselectivy to give optically active beta-lactams. The methods were applied to the synthesis of optically active carbapenem antibiotics such as (+) -PS-5, (+) -thienamycin and 1beta-methylcarbapenem.\n2. The 5-endo radical cyclization of N- (1-cyclohexenen-1-yl) -alpha-haloacetamides bearing a chiral auxiliary on the nitrogen atom was found to proceed with moderate degree of diastereoselectivy t give optically active octahydroindol-2-ones. The method was applied to the total synthesis of (-) -gamma-lycorane.\n3. The radical cyclization of N- (2-phenylthio-1-cyclohexenen-1-yl) -alpha-haloacetamies has been examined, and it was found that the course of the cyclizations was atrikingly affected by the reaction temperature employed. Thus, at room temperature, 4-exo cyclization predominated, and at higher temperature (in boiling toluene), 5-endo cyclization predominated.\n4. The kN-vinyl-2-bromobenzamides or N-vinyl-2- (2-bromophenyl) acetamides bearing a phenylthio group at the terminus of their N-vinylic bond were found to undergo radical cyclization in a 5-exo-trig or in a 6-exo-trig manner effectively to give isoindolone and isoquinolinones, respectively. The methods were applied to the synthesis of some alkaloids such as chilenine, lennoxamine, tetrahydropalmatine and saulatine.\n5. The N- [o- (2-propenyl) phenyl] -2,2-bis (phenylthio) acetamides were found to undergo radical cyclization in an 8-endo-trig manner to give benzoazocinone derivatives.","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:08672419, 研究期間(年度):1996 – 1997","subitem_description_type":"Other"},{"subitem_description":"出典：研究課題「高選択的ラジカル環化反応の確立と生理活性物質合成の応用」課題番号08672419\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-08672419/086724191997kenkyu_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":"金沢大学薬学部","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00066168","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/search/?qm=70028869"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/search/?qm=70028869","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-08672419/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-08672419/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-08672419/086724191997kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-08672419/086724191997kenkyu_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":"2022-05-30"}],"displaytype":"detail","filename":"PH-PR-ISHIBASHI-H-kaken 1999-3p.pdf","filesize":[{"value":"116.3 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"PH-PR-ISHIBASHI-H-kaken 1999-3p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/59917/files/PH-PR-ISHIBASHI-H-kaken 1999-3p.pdf"},"version_id":"f9e8ed11-be80-4e4e-bf04-648953505a88"}]},"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":"高選択的ラジカル環化反応の確立と生理活性物質合成の応用","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"高選択的ラジカル環化反応の確立と生理活性物質合成の応用"},{"subitem_title":"Establishment of Highly Selective Radical Cyclization and Application to the Synthesis of Biologically Active Compounds","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2836"],"pubdate":{"attribute_name":"公開日","attribute_value":"2022-05-30"},"publish_date":"2022-05-30","publish_status":"0","recid":"59917","relation_version_is_last":true,"title":["高選択的ラジカル環化反応の確立と生理活性物質合成の応用"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T12:59:40.563523+00:00"}