{"created":"2023-07-27T07:00:09.340954+00:00","id":59981,"links":{},"metadata":{"_buckets":{"deposit":"3bf56dc6-0d0e-4282-a3d4-363182bbcf44"},"_deposit":{"created_by":18,"id":"59981","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"59981"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00059981","sets":["2812:2813:2837"]},"author_link":["26426","105356"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1999-03-08","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"2p.","bibliographicVolumeNumber":"1995 – 1996","bibliographic_titles":[{"bibliographic_title":"平成8(1996)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":"1996 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":[{"creatorName":"Itaya, Taisuke"}],"nameIdentifiers":[{"nameIdentifier":"26426","nameIdentifierScheme":"WEKO"},{"nameIdentifier":"20019657","nameIdentifierScheme":"e-Rad","nameIdentifierURI":"https://kaken.nii.ac.jp/ja/search/?qm=20019657"}]}]},"item_9_description_21":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"筆者らが開発した2つの光学活性β, γ-不飽和アミノ酸誘導体の合成法のうち,ウィッティッヒ反応はケトンや脂肪族アルデヒドに対しては適用されておらず,ヘック反応は一般的なアリール体に対してはよい結果が得られていなかったので,これらの反応の一般的応用性を検討した.\n1.ウィッティッヒ反応の脂肪族アルデヒド,脂肪族ケトン及び芳香族ケトンへの適用は,カルボニルα位水素の存在に起因する副反応あるいはケトン類の反応性の低さのためか,成功しなかった.従って本法の適用は,芳香族アルデヒドに限定されることが分かった.\n2.窒素上の置換基をメトキシカルボニルとした分子内塩型ホスホニウムを用いるウィッティッヒ反応によって,酵母,高等植物あるいは哺乳類のフェニルアラニン転移リボ核酸微量塩基類の共通合成中間体の改良合成を実現した.\n3.この反応をヌクレオシドレベルに適用し,立体化学的に純粋な重要合成中間体を得ることに成功し,微量ヌクレオシドであるワイブトシンの実用的合成,ワイブトキソシンの最初の合成を可能にした.\n4.ビニルグリシンのヘック反応は水を溶媒とする場合でも炭酸水素ナトリウムを用いるのがよいことが分かった.このような反応条件下でも,複素環のヨウ化物や電子吸引性基をもつヨウ化ベンゼンとの反応は満足すべき結果を与えなかった.これに対して,ナフタレンや無置換あるいは電子供与性基を有するヨウ化ベンゼンでは95-98%eeの目的物が収率51-66%で生成した.\n以上の結果,いずれの方法も単独ではβ, γ-不飽和アミノ酸誘導体の一般合成法としては成立しなかったものの,光学純度の高い(E)-2-(アリールビニル)グリシン誘導体の優れた相補的合成法となることが判明した.","subitem_description_type":"Abstract"},{"subitem_description":"We have developed two methods for synthesis of optically active (E) -2- (arylvinyl) glcine derivatives.\n(1) In the present investigation N-protected 3- (triphenylphosphonio) alaninates are shown to be useful for the Witting reaction only with aromatic aldehydes : isobutyralehyde, cyclohexanone, and benzophenone proved unsuitable for this reaction.\n(2) Improved synthesis of the optically pure key intermediate for the synthesis of hypermodified bases of phenylalanine transfer ribonucleic acids was achieved by the Wittig reaction employing N- (methoxycarbonyl) -3- (triphenylphosphonio) alaninate.\n(3) The Wittig reaction described above was successfully applied to the synthesis at the nucleoside level. Thus, the most probable alternatives for the hypermodified nucleoside of rat liver phenylalanine transfer ribonucleic acid was synthesized for the forst time.\n(4) For the Heck reaction between (S) -N- (benzyloxycarbonyl) vinylglycine and 4-iodoanisole in H_2O,NaHCO_3O was shown to be best of the bases tested from a viewpoint of optical yield.\n(5) Scope and limitations of the Heck reaction described above was established in the present study.\nVarious (E) - (2-arylvinyl) glycines of 95-98% ee were obtained in highly stereoselective manners in 51-66% yields from phenyl, tolyl, anisyl, and naphthyl iodides. However, 2-, 3-, and 4-bromophenyl iodides provided the corresponding olefins of somewhat low optical purity (85-90% ee) in 30-51% yields ; iodobenzenes carying an electronwithdrawing 4-nitro or 4-acetyl group gave poor yields of products. Limited success was accomplished with iodides of heterocycles such as thiophene, imidazole, and imidazo [1,2-alpha] purin-9-ones.","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:07557289, 研究期間(年度):1995 – 1996","subitem_description_type":"Other"},{"subitem_description":"出典：研究課題「光学活性β, γ-不飽和アミノ酸の高立体選択的合成」課題番号07557289\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-07557289/075572891996kenkyu_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":"10.24517/00066232","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=20019657"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/search/?qm=20019657","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07557289/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07557289/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-07557289/075572891996kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-07557289/075572891996kenkyu_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_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"板谷, 泰助"}],"nameIdentifiers":[{"nameIdentifier":"105356","nameIdentifierScheme":"WEKO"},{"nameIdentifier":"20019657","nameIdentifierScheme":"e-Rad","nameIdentifierURI":"https://kaken.nii.ac.jp/ja/search/?qm=20019657"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2022-06-16"}],"displaytype":"detail","filename":"PH-PR-ITAYA-T-kaken 1999-2p.pdf","filesize":[{"value":"87.0 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"PH-PR-ITAYA-T-kaken 1999-2p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/59981/files/PH-PR-ITAYA-T-kaken 1999-2p.pdf"},"version_id":"c21c17b4-0f6a-40d9-aec6-e30758379f02"}]},"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":"光学活性β, γ-不飽和アミノ酸の高立体選択的合成","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"光学活性β, γ-不飽和アミノ酸の高立体選択的合成"},{"subitem_title":"Highly Stereoselective Syntheses of Optically Active beta, gamma-Unsaturated Amino Acids.","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2837"],"pubdate":{"attribute_name":"公開日","attribute_value":"2022-06-16"},"publish_date":"2022-06-16","publish_status":"0","recid":"59981","relation_version_is_last":true,"title":["光学活性β, γ-不飽和アミノ酸の高立体選択的合成"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2024-07-01T06:38:20.992241+00:00"}