{"created":"2023-07-27T07:01:04.166548+00:00","id":61215,"links":{},"metadata":{"_buckets":{"deposit":"5a9be82b-fc4d-465e-9163-368c1ac64740"},"_deposit":{"created_by":18,"id":"61215","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"61215"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00061215","sets":["2812:2813:2841"]},"author_link":["9747","10174"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1994-03-23","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"2p.","bibliographicVolumeNumber":"1991 – 1992","bibliographic_titles":[{"bibliographic_title":"平成4(1992)年度 科学研究費補助金 一般研究(C) 研究成果報告書概要"},{"bibliographic_title":"1992 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":"本研究では,アシルシランシリルエノールエーテル(I)とアセタール類との反応による3-アルコキシアシルシラン誘導体の立体選択的生成と,これを利用する3または4連続不斉中心の選択的構築法について検討した。\nカルボニル基のα位にメチレン基を有するアシルシランをエノール化させ,生じたエノラートを塩化シランで捕捉してIを良好な収率で得た。エノール化剤としてのLDAの使用はZおよびE-Iの混合物を,ホスホニウムジイリドではE-Iを立体選択的に得た。\nE-またはZ-Iとアルデヒドジメチルアセタール類のアルドール反応ではいずれのIからも2,3-anti-3-メトキシ-1-シリル-1-アルカノン(II)が優先的に生じた。また,エーテル炭素置換基がフェニル及び直鎖アルキル基のIとベンズアルデヒドアセタールとの反応で最も高い立体選択性(d.e=92-96%)が認められた。\nE-Iとd,1-フエニルプロピオンアルデヒドジメチルアセタールアルドールとの反応では,3連続不斉中心を有する2,3-syn-3,4-syn-3-メトキシアシルシラン(V)が高立体選択的に生成し,3,4位炭素の相対配置とともに2,3位炭素のそれも規制されることが明らかとなった。\nIIおよびVにアルキルまたはフェニルリチウムを反応させ,対応する3および4連続不斉中心を持つ3-メトキシ-1-シリル-1-アルカノール(IIIおよびVI)を定量的かつ高ジアステレオ選択的に得た(d.e=80-99%)。IIIおよびVIのフッ素アニオン試薬による脱シリルプロトン化は,2,3位炭素間の相対立体配置に関係なく,定量的かつ立体特異的に進み対応する1,2-anti-3-メトキシ-1-アルカノール(IVおよびVII)を生じた(d.e=>99%)。","subitem_description_type":"Abstract"},{"subitem_description":"There has been considerable interest in recent years in the stereoselective formation of multiple chiral centers using aldol reaction between prochiral enolates and aldehydes. We disclosed here an convenient method of diastereoselective construction of the three or four contiguous chiral centers using the Lewis acid mediated reaction of acylsilane silyl enol ethers (I) with acetals and the subsequent nucleophilic addition to the carbonyl group of the resulting acylsilanes (II).\nTreatment of E-or Z-acylsilane silyl enol ethers (I) derived from acylsilanes having enolizable methylene proton with a mixture of aldehyde dimethylacetals and TiCl_4 in dichloromethane gave the corresponding 2,3-anti-3-methoxy-1-silyl-1-alkanones (II) in high diastereo excess,independent of the double bond stereochemistry of I used. The similar reaction of E-I with d,1-phenylpropionealdehyde afforded 2,3-syn-3,4-syn-3-methoxy-1-silyl-1-butanal (V) in high stereoselectivity.\nThe resulting acylsilane 2,3-anti-II and 2,3-syn-3,4-syn-V were subjected to the nucleophilic reaction with alkyl or phenyllithium to yield the corresponding 3-methoxy-1-silyl-1-alkanols with three and four contiguous asymmetric centers (III and VI, respectively) stereoselectively. The protiodesilylation of III and VI with F^- reagent to afford the corresponding 1,2-anti-al- kanols with three and four contiguous asymmetric centers, IV and VII in 95-99% diastereo excess.","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:03650694, 研究期間(年度):1991 – 1992","subitem_description_type":"Other"},{"subitem_description":"出典：研究課題「アシルシランシリルエノールエーテルのアルドール反応による連続不斉中心の選択的生成」課題番号03650694\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-03650694/036506941992kenkyu_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":"金沢大学工学部","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00067459","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=70019735"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/search/?qm=70019735","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-03650694/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-03650694/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-03650694/036506941992kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-03650694/036506941992kenkyu_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":"2022-10-24"}],"displaytype":"detail","filename":"TE-PR-NAKAJIMA-T-kaken 1994-2p.pdf","filesize":[{"value":"83.1 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"TE-PR-NAKAJIMA-T-kaken 1994-2p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/61215/files/TE-PR-NAKAJIMA-T-kaken 1994-2p.pdf"},"version_id":"d3305c79-64a3-4113-9498-1f0402496c6c"}]},"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":"アシルシランシリルエノールエーテルのアルドール反応による連続不斉中心の選択的生成","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"アシルシランシリルエノールエーテルのアルドール反応による連続不斉中心の選択的生成"},{"subitem_title":"Diastereoselective Construction of Contiguous Chilal Centers by the Aldol Reaction of Acylsilane Silyl Enol Ethers.","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2841"],"pubdate":{"attribute_name":"公開日","attribute_value":"2022-10-24"},"publish_date":"2022-10-24","publish_status":"0","recid":"61215","relation_version_is_last":true,"title":["アシルシランシリルエノールエーテルのアルドール反応による連続不斉中心の選択的生成"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T12:06:22.487068+00:00"}