{"created":"2023-07-27T07:01:23.476090+00:00","id":61673,"links":{},"metadata":{"_buckets":{"deposit":"abc51abd-162a-45cd-b18b-3f7a58a1132e"},"_deposit":{"created_by":18,"id":"61673","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"61673"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00061673","sets":["2812:2813:2846"]},"author_link":["18554"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1989-03-29","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"2p.","bibliographicVolumeNumber":"1986 – 1987","bibliographic_titles":[{"bibliographic_title":"昭和62(1987)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":"1987 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":"Suga, Sohei"}],"nameIdentifiers":[{"nameIdentifier":"18554","nameIdentifierScheme":"WEKO"},{"nameIdentifier":"40019691","nameIdentifierScheme":"e-Rad","nameIdentifierURI":"https://kaken.nii.ac.jp/ja/search/?qm=40019691"}]}]},"item_9_description_21":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"光学活性な有機リン化合物は, 不斉水素化触媒の配位子として重要な役割を演じ, 生体内でもP-C結合を有する化合物が数多く発見され, そのほとんどが生体の重要な機能をつかさどっている. このような有機リン化合物の合成法はいくつか報告されているが, ほとんどの場合反応操作が煩雑で古典的な光学分割法によるものであり, 従来の合成法にかわるより簡便な, しかも高い立体選択性を有する反応経略を確立することは意義深い. そこで本研究では, 各種ジクロロホスフィンRPcl_2(R=Ph,Me,OPh,O^〓r,SEt,SPh等)と(S)-プロリノールをトリエチルアミン存在下反応させ, 対応する3価のリン化合物(I)を合成した. Iのジアステレオマー比は用いたRPcl_2のRによって異なるが, アルキル基やアリール基の場合には一方の異性体のみが得られた. 次にIを異性体混合物のまま, 種々のハロゲン化アルキルとアルブゾフ反応させ, P-C結合の生成と同時に位置選択的に環内のP-O結合を開裂させ, 対応する5価のリン化合物(II)に変換した. この段階で生じたジアステレオマーをジリカゲルのカラムクロマトにより, ほぼ完全に分離できた. ついで単離したIIの各異性体を硫酸またはトリフオロメタンスホン酸存在下, 加アルコール分解により, 立体配置反転で不斉源を除去し, 目的の光学治性ホスフィネート, ホスホネート, ホスホノチオエート等を得た. また, これらのリン化合物は光学的にほぼ純粋であることを, キラルシフト試薬を用いる｀H-NMR法によって明らかにした. しかも光学活性リン化合物の絶対配置とシフト試薬によるシグナル分離のパターンとの間の相関についての経験則が確立された.\n以上, 環状リン化合物のアルブゾフ反応を利用して, 様々な光学活性有機リン化合物が簡便に合成できるようになり, 本合成法が一般性のあることを明らかにした.","subitem_description_type":"Abstract"},{"subitem_description":"Optically active organophosphorus compounds have occupied a key position in the stereochemical investigations of nucleophilic substitutions at phosphoryl centers and the study of ligands in transition metal complexes used as asymmetric homogeneous catalysts. A general and practical method for the preparation of these phosphorus compounds has been limited to a few examles. We have investigated a novel synthetic route involving Arbuzov reaction of trivalent cyclic phosphorus compounds, and reported the synthesis of optically active phosphine oxides. In this project, we wish to report a new and convenient method for the preparation of optically active organophosphorus compounds in high enantiomeric purity using Arbuzov reaction of cyclic trivalent 1,3,2-oxazaphospholidine derivatives.\nThe Arbuzov reaction of trivalent cyclic phosphorus compound, which was synthesized by the reaction of (S)-prolinol with some chlorophosphines RPCl_2 in the presence of trietylamine, with a variety of alkyl halides gave the corresponding pentavalent ringopening compounds with regioselective cleavage of the endo C-O bond as a mixture of diastereomers. After the separation of isomers by column chromatography over silica gel, acid-catalyzed alcoholysis of each diasteremeric isomer resulted in P-N bond cleavage with inversion of configuration at phosphorus atom to afford many kinds of enantiomerically pure organophosphorus compounds. The optical purities of these compounds were measured by a ^1 H-NMR method using a chiral shift reagent.","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:61550631, 研究期間(年度):1986 – 1987","subitem_description_type":"Other"},{"subitem_description":"出典：研究課題「5員環リン化合物のアルブゾフ反応を利用する光学活性リン化合物の簡便な合成法の開発」課題番号61550631\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-61550631/615506311987kenkyu_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":"10.24517/00067916","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=40019691"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/search/?qm=40019691","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-61550631/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-61550631/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-61550631/615506311987kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-61550631/615506311987kenkyu_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":"須賀, 操平"}],"nameIdentifiers":[{"nameIdentifier":"18554","nameIdentifierScheme":"WEKO"},{"nameIdentifier":"40019691","nameIdentifierScheme":"e-Rad","nameIdentifierURI":"https://kaken.nii.ac.jp/ja/search/?qm=40019691"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2022-11-11"}],"displaytype":"detail","filename":"TE-PR-SUGA-S-kaken 1989-2p.pdf","filesize":[{"value":"84.6 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"TE-PR-SUGA-S-kaken 1989-2p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/61673/files/TE-PR-SUGA-S-kaken 1989-2p.pdf"},"version_id":"254c9d4d-fe17-4e7c-8849-dcb21fa64fbe"}]},"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":"5員環リン化合物のアルブゾフ反応を利用する光学活性リン化合物の簡便な合成法の開発","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"5員環リン化合物のアルブゾフ反応を利用する光学活性リン化合物の簡便な合成法の開発"},{"subitem_title":"A Facile Preparation of Optically Active Organophosphorus Compounds Using Arbuzov Reaction of Five-membered Ring Phosphorus Compounds","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2846"],"pubdate":{"attribute_name":"公開日","attribute_value":"2022-11-11"},"publish_date":"2022-11-11","publish_status":"0","recid":"61673","relation_version_is_last":true,"title":["5員環リン化合物のアルブゾフ反応を利用する光学活性リン化合物の簡便な合成法の開発"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2024-07-01T06:54:12.507971+00:00"}