{"created":"2023-07-27T06:44:29.041872+00:00","id":34724,"links":{},"metadata":{"_buckets":{"deposit":"50fb19c8-2ce0-44ed-ab07-0c716dbed94b"},"_deposit":{"created_by":3,"id":"34724","owners":[3],"pid":{"revision_id":0,"type":"depid","value":"34724"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00034724","sets":["2812:2813:2826"]},"author_link":["200"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2008-05-01","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"13p.","bibliographicVolumeNumber":"2006-2007","bibliographic_titles":[{"bibliographic_title":"平成19(2007)年度 科学研究費補助金 基盤研究(C) 研究成果報告書"},{"bibliographic_title":"2007 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":"1,3-ジエニルスルホンにアミンの求核付加反応を行なったところ,非環状の第二級アミンを用い,THFなどの立体障害が比較的小さく極性の高いエーテル系の溶媒中で反応を行なうと,立体化学的には不利と考えられる(Z)-アリルスルホンが優先して得られることを見出した。アミンの濃度が低いほど,また,大変興味深いことに温度が高いほど,Z選択性が高くなることを明らかにした。この現象は,アミンが1,3-ジエニルスルホンのδ位を攻撃してγ位に電子を供給するとき,syn型遷移状態の安定性の違い(\"シン効果\"),即ち,γ-炭素上に生じるn電子対とC_α=C_βのπ^*軌道との間のη→π^*相互作用および,γ位のC-H結合のσ軌道とC_α=C_βのπ^*軌道との間のσ_<C-H>→π^*相互作用に基づいて説明できることを示した。電子求引基としてスルホンに換え,エステルを有する(E)-2,4-ペンタジエン酸エチルの場合にも,立体化学的には不利と考えられる(Z)-5-アミノ-3-ペンテン酸エチルが優先して得られることを見出した。 一方,酸素官能基を有する基質の異性化反応では,\"シン効果\"が強く作用し,極めてZ選択性が高い。そこで,得られたZ-ビニルエーテルから[1,2]Wittig転位を行ない新たな炭素炭素結合反応を試みたところ,δ位の置換基がBn0基(Bn=PhCH_2)のビニルオキシランおよびアリル型スルホンに過剰量の塩基を作用させたところ,1,4-脱離型反応に引続き[1,2]Wittig転位が進行し,対応するZ,E体のジエニルアルコールを立体選択的に得ることができた。","subitem_description_type":"Abstract"},{"subitem_description":"Stereochemistry of the 1,4-eliminative ring opening of [3-substituted (E) -1-propenyl]oxiranes to the corresponding 2,4-dienyl alcohols by LDA was investigated. The Z/E ratios of the resulting 2, 4-dienyl alcohols varied with the substituents at 3-position of the propenyl group. This phenomenon was discussed based on the concept of a \"syn-effect,\" which is most primarily rationalized by a σ→π* interaction.\nStereochemistry of nucleophilic addition of amines to (E) -1-tosyl-l,3-butadiene was investigated. The Z/E ratios of the resulting allylic sulfones varied with amines, solvents, temperature, and concentration. When diethylamine was reacted in low concentration at higher temperature, the corresponding sterically unfavorable (Z) -4-amino-2-butenyl sulfone was preferentially obtained. Stereochemistry of nucleophilic addition of amines to ethyl (E)-2,4-pentadienoate, which possesses an ester group as a conjugated electron-withdrawing group instead of p-toluenesulfonyl(Ts) group, was also investigated to realize similar high (Z)-selectivity. The predominant formation of (Z)-isomers in both cases was rationalized by a \"syn-effect,\" which might be mainly due to n/σ→π* interaction and/or 6r-electron homoaromaticity.\nIn the case of δ-benzyloxy substituted vinyloxiranes, [1,2]-Wittig rearrangement proceeded following the initial 1,4-eliminative ring opening to give a (E,Z) -2,4-dienyl 1,6-diols in a completely stereoselective manner. The sequential 1,4-eliminative ring opening-[1,2]-Wittig rearrangement also proceeded using α, α-dimethyl allylic sulfones to give the corresponding (Z)-dienyl alcohols.","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:18550030, 研究期間(年度):2006–2007","subitem_description_type":"Other"},{"subitem_description":"出典：「シン効果の本質解明と応用」研究成果報告書　課題番号18550030\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":"10.24517/00034711","subitem_identifier_reg_type":"JaLC"}]},"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-18550030/","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-18550030/185500302007kenkyu_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 2008-13p.pdf","filesize":[{"value":"626.5 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-UKAJI-Y-kaken 2008-13p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/34724/files/SC-PR-UKAJI-Y-kaken 2008-13p.pdf"},"version_id":"c1b26cb7-1ddf-42e1-a3cf-a42b02fd47a2"}]},"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":"シン効果の本質解明と応用","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"シン効果の本質解明と応用"},{"subitem_title":"Elucidafion of Origin of\"Syn-Effect\" and Application to Organic Synthesis","subitem_title_language":"en"}]},"item_type_id":"9","owner":"3","path":["2826"],"pubdate":{"attribute_name":"公開日","attribute_value":"2017-10-05"},"publish_date":"2017-10-05","publish_status":"0","recid":"34724","relation_version_is_last":true,"title":["シン効果の本質解明と応用"],"weko_creator_id":"3","weko_shared_id":3},"updated":"2023-07-27T14:24:56.749108+00:00"}