{"created":"2023-07-27T06:44:34.409817+00:00","id":34846,"links":{},"metadata":{"_buckets":{"deposit":"2e1a774a-7644-469f-a769-a60b63ecd822"},"_deposit":{"created_by":3,"id":"34846","owners":[3],"pid":{"revision_id":0,"type":"depid","value":"34846"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00034846","sets":["2812:2813:2834"]},"author_link":["200"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2000-03-01","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"8p.","bibliographicVolumeNumber":"1998-1999","bibliographic_titles":[{"bibliographic_title":"平成11(1999)年度 科学研究費補助金 基盤研究(C) 研究成果報告書"},{"bibliographic_title":"1999 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":"有用な生理活性を有する光学活性化合物の合成には任意の立体化学を有する光学活性化合物の合成法の確立が必要である。本研究では、両鏡像体共に入手容易な酒石酸エステルより調製される二核キラル反応場を設計し、種々の反応に対応できる触媒的不斉合成反応系の確立を試みた。 γ位にエステル置換基を持つE体のアリルアルコールへのニトリルオキシド不斉1,3-双極付加環化反応を試みたところ、高い光学純度でtrans体の3,4,5-三置換-2-イソオキサゾリンを得ることができた。このtrans体の2-イソオキサゾリンは電子吸引性のエステル置換基の特徴を生かして、少量のDBUを作用させることによりcis体の2-イソオキサゾリンへ変換できることを見出した。従って、酒石酸エステルが両鏡像体ともに入手容易であることを考え合わせると、単一の出発物質から、簡便な方法で任意の立体化学を有する3,4,5-三置換-2-イソオキサゾリンが合成できる。 一方、イミン類への不斉求核付加反応の開発にも取り組み、ジエチル亜鉛とヨード酢酸エステルから調製されたReformatsky型試薬のイソキノリン骨格を有するニトロンへの不斉求核付加反応がエナンチオ選択的に進行することを見出した。さらに、基質としてo-アミノフェノールとアルデヒドから得られる非環状イミンを選び、Reformatsky型試薬による不斉求核付加反応を試みたところ、対応するβ-アミノ酸誘導体が高い光学純度で得られた。この反応では、水の添加が再現性の良い高光学純度の達成に必須である、という大変興味深い事実を見出した。 本研究は立体化学を任意に制御して各種光学活性化合物を合成できる画期的なものであり、有機合成化学に留まらず、医学、薬学、農学などの関連諸分野の21世紀に向けての飛躍的発展に大きく貢献できるものと考えられる。","subitem_description_type":"Abstract"},{"subitem_description":"It is strongly required to develop a practical and efficient method for the construction of chiral molecules to explore new biologically active medicines and agricultural chemicals. In this research, a new and novel chiral system possessing two metal centers utilizing tartaric acid esters was designed ; that is, if two reactants are bound to two different metal centers of the dialkoxide derived from tartaric acid ester, which might actually form the rigid 5/5-fused bicyclic dinucleating structure, they might be ideally oriented and/or activated by the metals and the following reaction might proceed in an enantioselective manner to afford the corresponding optically active products.\nThe asymmetric 1,3-dipolar cycloaddition of nitrile oxides to ethyl (E)-4-hydroxy-2-butenoate was achieved by the use of diisopropyl (R,R)-tartrate as a chiral auxiliary to afford the corresponding 4,5-trans-2-isoxazolines, which were transformed to the corresponding 4,5-cis-2-isoxazolines by the treatment with a base through isomerization and lactonization.\nThe asymmetric addition of the Reformatsky-type reagent, prepared in situ from diethylzinc and iodoacetic acid ester, to a carbon-nitrogen double bond in 3,4-dihydroisoquinoline N-oxides was achieved with enantioselectivity up to 86% ee. Furthermore, the asymmetric addition of the Reformatsky-type reagent to imines prepared from aldehydes and 2-aminophenol was also achieved to give β-amino acid derivatives. In order to realize reproducible higher stereoselection, the addition of a small amount of water was crucial.","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:10640515, 研究期間(年度):1998–1999","subitem_description_type":"Other"},{"subitem_description":"出典：「酒石酸エステルを活用する二核キラル反応場の構築と光学活性化合物合成への応用」研究成果報告書　課題番号10640515\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":"10.24517/00034833","subitem_identifier_reg_type":"JaLC"}]},"item_9_publisher_17":{"attribute_name":"公開者","attribute_value_mlt":[{"subitem_publisher":"金沢大学自然科学研究科"}]},"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=80193853","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640515/","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-10640515/106405151999kenkyu_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":"SC-PR-UKAJI-Y-kaken 2000-8p.pdf","filesize":[{"value":"354.2 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-UKAJI-Y-kaken 2000-8p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/34846/files/SC-PR-UKAJI-Y-kaken 2000-8p.pdf"},"version_id":"8b851d75-bc51-4726-9e19-feb74bd87155"}]},"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":"酒石酸エステルを活用する二核キラル反応場の構築と光学活性化合物合成への応用","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"酒石酸エステルを活用する二核キラル反応場の構築と光学活性化合物合成への応用"},{"subitem_title":"Design of a Chiral Dinucleating System Utilizing Tartaric Acid Ester as a Chiral Auxiliary and Its Application to the Synthesis of Optically Active Compounds","subitem_title_language":"en"}]},"item_type_id":"9","owner":"3","path":["2834"],"pubdate":{"attribute_name":"公開日","attribute_value":"2017-10-05"},"publish_date":"2017-10-05","publish_status":"0","recid":"34846","relation_version_is_last":true,"title":["酒石酸エステルを活用する二核キラル反応場の構築と光学活性化合物合成への応用"],"weko_creator_id":"3","weko_shared_id":3},"updated":"2023-07-27T14:49:03.687882+00:00"}