{"created":"2023-07-27T06:52:45.140984+00:00","id":46857,"links":{},"metadata":{"_buckets":{"deposit":"f6ca5a94-7484-499f-b042-e71e77036c88"},"_deposit":{"created_by":18,"id":"46857","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"46857"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00046857","sets":["2812:2813:2833"]},"author_link":["81648","81647"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2001-03","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"98p.","bibliographicVolumeNumber":"1999-2000","bibliographic_titles":[{"bibliographic_title":"平成12(2000)年度 科学研究費補助金 基盤研究(C) 研究成果報告書"},{"bibliographic_title":"2000 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":"周期表の様々な元素の特性を活用した選択的かつ効率的な分子変換反応の開発研究の一環として、ジルコニウムやチタン、亜鉛、銅およびセレンの各元素のもつ潜在的な反応特性を相乗的に生かした反応を組み合わせ、有機合成上有用な官能基を有する化合物へ効率よく変換することを検討した。\nα位あるいはβ位にフェニルセレノ基を有する末端アルキン(1)とSchwartz試薬とのヒドロジルコネーションは、位置および立体選択的に付加反応が進行し、トランス形の末端ビニルジルコノセン誘導体を与えた。引き続き高次有機銅試薬およびジメチル亜鉛とのトランスメタル化反応により系中にフェニルセレノ基を有するビニル銅やビニル亜鉛中間体を生成させ、これとエノン類やエポキシド、アルデヒドとの反応を行った結果、良好な収率で1,4-付加生成物やアリルアルコール誘導体等を与えることを明らかにした。また、ブチルリチウムによる1の末端水素の引き抜きによりsp炭素アニオンを生成させ、引き続き求電子剤との反応および酸化反応を行った結果、アリルアルコールやジエンおよび3,4-ジヒドロキシ-1-アルケンやエンイン部位をもつアルコール誘導体などの有用な官能基に変換できることを明らかにした。一方、アルデヒドから容易に合成できるフェニルセレノールエステルとジメチルチタノセンとの反応をトルエン中行うと、カルボニル基のメチレン化が進行し、対応するビニルセレニドが中程度の収率で得られることを示した。さらに、これらをm-CPBAで酸化後塩基存在下加熱すると、セレノキシド脱離が位置選択的に進行し、末端アルキンが生成することを明らかにした。この一連の反応において、アルデヒド基が増炭を伴い炭素-炭素三重結合に変換されたことになる。","subitem_description_type":"Abstract"},{"subitem_description":"Terminal alkynes (1) having a PhSe group on α or β carbonn atom contain three reactive sites (C-C triple bond, terminal alkynic hydrogen atom, PhSe group). Generally, hydrometalation of terminal alkynes takes place stereospecifically to give the E-alkenic metal species which are replaced by some electrophiles such as aldehydes, epoxides, and acyl halides to construct a new carbon-carbon bond. On the other hand, organoselenium chemistry became a very powerful tool in organic synthesis in recent times. Of particular importance is the owing to its easily handled nature.\n1 reacted with zirconocene-ethylene complex to give regioselectively zirconacyclopentene derivatives. Hydrozirconation of 1 with Cp_2ZrHCl followed by transmetalation with Me_2Zn gave the corresponding terminal vinylzinc intermediates regio-and stereoselectively, which underwent the coupling reaction with aldehydes to afford the allylic alcohol derivatives having a phenylseleno group. Terminal hydrogen atom of 1 was easily abstracted by n-BuLi at-78℃ to generate sp carbanion species which were effectively trapped by aldehydes on epoxides. The compounds with a phenylseleno group were oxidized with excess amounts of H_2O_2 to yield the desired products having A-shaped olefinic alcohol moiety in good yields via selenoxide syn elimination.\nMethylenation of phenylselenolesters with dimethyl titanocene (Cp_2TiMe_2) gave alkenyl selenides, which were subjected to oxidation with m-CPBA to afford terminal alkynes, not to allene, via selenoxide syn elimination. On the other hand, reaction of α-phenylseleno ketones with Cp_2TiMe_2 gave a mixture of isomeric allylic selenides and the subsequent oxidation by H_2O_2 led to the formation of allylic alcohols via [2,3] sigmatropic rearrangement.","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:11650888, 研究期間(年度):1999-2000","subitem_description_type":"Other"},{"subitem_description":"出典：「複数の元素の協同作用を利用する多官能性分子構築法の開発」研究成果報告書　課題番号11650888\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":"10.24517/00053184","subitem_identifier_reg_type":"JaLC"}]},"item_9_publisher_17":{"attribute_name":"公開者","attribute_value_mlt":[{"subitem_publisher":"金沢大学理工研究域物質化学系"}]},"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=90135046"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/search/?qm=90135046","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650888/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650888/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-11650888/116508882000kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-11650888/116508882000kenkyu_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":"2019-02-14"}],"displaytype":"detail","filename":"SC-PR-SEGI-M-kaken 2001-98p.pdf","filesize":[{"value":"1.6 MB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-SEGI-M-kaken 2001-98p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/46857/files/SC-PR-SEGI-M-kaken 2001-98p.pdf"},"version_id":"be0e104b-6291-48e4-b216-03843626187d"}]},"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":"複数の元素の協同作用を利用する多官能性分子構築法の開発","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"複数の元素の協同作用を利用する多官能性分子構築法の開発"},{"subitem_title":"Synthesis of Polyfunctionalyzed Molecules Using Cooperative Interactions between Multiple Elements","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2833"],"pubdate":{"attribute_name":"公開日","attribute_value":"2019-02-14"},"publish_date":"2019-02-14","publish_status":"0","recid":"46857","relation_version_is_last":true,"title":["複数の元素の協同作用を利用する多官能性分子構築法の開発"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T14:47:08.357337+00:00"}