{"created":"2023-07-27T06:44:30.982613+00:00","id":34768,"links":{},"metadata":{"_buckets":{"deposit":"ce9b55d0-86c1-4216-9658-78ef493c326d"},"_deposit":{"created_by":3,"id":"34768","owners":[3],"pid":{"revision_id":0,"type":"depid","value":"34768"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00034768","sets":["2812:2813:2828"]},"author_link":["200"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2006-05-01","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"10p.","bibliographicVolumeNumber":"2004-2005","bibliographic_titles":[{"bibliographic_title":"平成17(2005)年度科学研究費補助金 基盤研究(C) 研究報告書"},{"bibliographic_title":"2005 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":"本研究では,構成する原子全てが生成物に含まれることからアトムエコノミーの点で非常に優れた不斉付加環化反応の革新を目的に,両鏡像体ともに入手可能な酒石酸エステル由来の複核キラル反応場において高効率的な各種エナンチオ選択的付加環化反応の実現を試み,以下の成果を挙げた。 1.金属として亜鉛を用い,アミド置換基を有し,窒素上にp-メトキシフェニル(An)基を導入したニトロンの触媒的不斉1,3-双極子付加環化反応を試み,さらに(2S,4R)-4-hydroxyornithineの合成前駆体へと変換することができた。 2.亜鉛原子を二つ有するキラル反応場設計により,触媒的ニトロソ化合物の不斉ヘテロDiels-Alder反応に成功した。 3.ベンゾシクロブテノールから発生するo-キノジメタンの不斉Diels-Alder反応の開発を行ない,金属としてマグネシウム,亜鉛を用いる設計により,フマル酸ジエチルとのDiels-Alder反応がジアステレオおよびエナンチオ選択的に進行することを見出した。 4.酒石酸エステルのメチル亜鉛塩を活用する複核キラル反応場設計により,ニトロンへの亜鉛アセチリドの不斉求核付加反応により,対応する光学活性N-(プロパルギル)ヒドロキシルアミンが得られ,さらに反応中間体をそのまま昇温すると,分子内環化反応が引き続き進行し,対応する4-イソオキサゾリンが生成することを明らかにした。この反応では,添加剤を加えると光学純度が飛躍的に向上するという新奇な不斉増幅を観察することができた。さらに,触媒的な系に展開も可能であるという知見も得ることができた。","subitem_description_type":"Abstract"},{"subitem_description":"In order to develop a practical method for the construction of chiral molecules, we have designed a novel chiral system possessing multi-metal centers utilizing tartaric acid ester as a chiral auxiliary.\nA catalytic asymmetric 1,3-dipolar cycloaddition of nitrones possessing the N,N-diisopropylamide moiety to allylic alcohols was achieved to afford di- or trisubstituted isoxazolidines with excellent enantioselectivity of up to over 99% ee. The present asymmetric 1,3-dipolar cycloaddition was applied to the synthesis for the (2S,4R)-4-hydroxyornithine derivative.\nThe regio- and enantioselective hetero Diels-Alder reaction of nitroso compound with dienol has been realized utilizing a catalytic amount of tartaric acid ester as a chiral auxiliary and the corresponding cycloadduct was obtained in complete regioselectivity with excellent enantioselectivity up to 84% ee.\nThe asymmetric Diels-Alder reaction of o-quinodimethanes, generated from benzocyclobutenols in situ, with fumaric acid esters was achieved by utilizing diisopropyl (R,R)-tartrate as a chiral auxiliary to afford the corresponding optically active 1,2-cis-substituted 1-hydroxy tetrahydronaphthalene derivatives with enantioselectivity up to 83% ee.\nThe asymmetric addition of alkynylzinc reagents, prepared in situ from dialkylzinc and 1-alkynes, to nitrones was achieved by utilizing di(t-butyl) (R,R)-tartrate as a chiral auxiliary to afford the corresponding optically active (R)-α-substituted propargylic N-hydroxylamines. By the addition of product-like N-hydroxylamine, unprecedented enhancement of enantioselectivity was observed to afford the N-hydroxylamines up to 95% ee.","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:16550031, 研究期間(年度):2004–2005","subitem_description_type":"Other"},{"subitem_description":"出典：「複核キラル反応場における複合的制御を基盤とする不斉付加環化反応の革新」研究成果報告書　課題番号16550031   (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":"10.24517/00034755","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-16550031/","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-16550031/165500312005kenkyu_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 2006-10p.pdf","filesize":[{"value":"485.7 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-UKAJI-Y-kaken 2006-10p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/34768/files/SC-PR-UKAJI-Y-kaken 2006-10p.pdf"},"version_id":"f3cd6d31-21eb-46b0-b33a-7245afc8b45a"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"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":"複核キラル反応場における複合的制御を基盤とする不斉付加環化反応の革新","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"複核キラル反応場における複合的制御を基盤とする不斉付加環化反応の革新"},{"subitem_title":"Innovation of Asymmetric Cycloaddition Reactions Based on Highly Efficient Stereocontrol in Multinucleating Chiral Reaction Field","subitem_title_language":"en"}]},"item_type_id":"9","owner":"3","path":["2828"],"pubdate":{"attribute_name":"公開日","attribute_value":"2017-10-05"},"publish_date":"2017-10-05","publish_status":"0","recid":"34768","relation_version_is_last":true,"title":["複核キラル反応場における複合的制御を基盤とする不斉付加環化反応の革新"],"weko_creator_id":"3","weko_shared_id":3},"updated":"2023-07-27T14:32:01.539453+00:00"}