{"created":"2023-07-27T06:52:45.095766+00:00","id":46856,"links":{},"metadata":{"_buckets":{"deposit":"359e8b12-bab9-427e-9f73-ee58175c920a"},"_deposit":{"created_by":18,"id":"46856","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"46856"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00046856","sets":["2812:2813:2830"]},"author_link":["81648","81647"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2004-03","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"134p.","bibliographicVolumeNumber":"2002-2003","bibliographic_titles":[{"bibliographic_title":"平成15(2003)年度 科学研究費補助金 基盤研究(C) 研究成果報告書"},{"bibliographic_title":"2003 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、PdやZrおよびSeの各元素のもつ潜在的な反応特性を各々生かした反応を複合的に組み合わせ、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。\nフェニルホモプロパルギルセレニド(1)とCp_2ZrHCl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進行し、定量的に末端ビニルジルコノセン中間体を与え、さらにPd(0)触媒存在下ヨウ化アリールあるいはヨウ化アルケニルとのカップリング反応により、E配置を有するスチレン及びジエン誘導体が高収率で得られた。引き続き過酸化水素で酸化するとセレノキシド脱離が進行し、ほぼ純粋なE配置をもつジエンやトリエン化合物を与えることを明らかにした。また、1とE-ヨードアルケンとの薗頭反応とそれに続く酸化反応を順次行うと、良好な収率で共役エンインエン化合物が得られた。同様な手法により異性体であるジエンイン化合物も合成できた。\n炭素数の1つ少ないフェニルプロパルギルセレニド(2)と1当量のn-BuLiとの反応は末端アルキン水素が引き抜かれ、引き続くアルデヒドやシリルクロリドとの反応により三重結合の末端で官能基化が効率よく進行した。得られた化合物をm-CPBAで酸化すると、[2,3]シグマトロピー転位が進行したと考えられるアレニルアルコール誘導体を経由し、さらに異性化したエノン体を与えた。一方、2は2当量のLDAよりジアニオン種を生成し、引き続くアルデヒドとの反応によりセレン原子のα位で位置選択的な炭素-炭素結合形成が起こることを明らかにした。さらに上記1と同様m-CPBAによる酸化反応ではエノン誘導体が得られ、このうちE-体の化合物は分子内ヘミアセタール化により2-ヒドロキシー2,5-ジヒドロフラン体を与えた。","subitem_description_type":"Abstract"},{"subitem_description":"Terminal alkynes having a PhSe group on a or β carbon atom contain some reactive sites (C-C triple bond, acidic protons, phenylseleno group) and has potential as a synthetic precursor to highly functionalized compounds. Hydrozirconation of homopropargyl phenyl selenide (1)with Schwartz's reagent gave the corresponding terminal vinylzirconocene regio-and stereoselectively. This zirconocene intermediate was successively subjected to Stille-type coupling with aryl or alkenyl iodides in the presence of Pd(0) catalyst, followed by oxidative removal of the phenylseleno group via selenoxide syn elimination to afford conjugated polyene compounds with E-configuration in good yields. Phenyl propargyl selenide (2)was easily deprotonated by 2 equiv of LDA in THF at -78℃ to give a solution of the dianion reagent. Aldehydes reacted with the dianion exclusively at the a position of selenium atom to afford homopropargyl alcohol derivatives. Oxidation of these compounds with 1 equiv of m-CPBA gave the corresponding selenoxides, which underwent the [2,3] sigmatropic rearrangment to yield α-phenylseleno-substituted enone derivatives, presumably via allenyl alcohol intermediates. E-isomers of enone compounds were followed by cyclization via an intramolecular hemiacetalization to give 2-hydroxy-2,5-dihydrofuran derivatives. Interestingly, the addition of pyridine to the reaction mixture led to an exclusive formation of the dihydrofuran compounds. Thus, the dianion of 2 served as a synthetic equivalent of acrolein dianion, and the two anionic centers can be utilized separately. The similar oxidation of silylated propargyl selenide derivatives resulted in the formation of α,β-unsaturated acylsilanes in good yields. Silylated homopropargyl alcohol derivatives were oxidized by m-CPBA to give 2-silyl-3-phenylselenofuran compounds and γ-hydroxy-substituted Z-α,β-unsaturated acylsilanes. The former may be obtained via an intramolecular cyclization of the corresponding E-α,β-unsaturated acylsilanes followed by the dehydration.","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:14550822, 研究期間(年度):2002-2003","subitem_description_type":"Other"},{"subitem_description":"出典：「金属及びヘテロ元素の反応特性を複合的に活用した効率的分子変換反応の開発」研究成果報告書　課題番号14550822\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":"10.24517/00053183","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-14550822/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550822/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-14550822/145508222003kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-14550822/145508222003kenkyu_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 2004-134p.pdf","filesize":[{"value":"2.1 MB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-SEGI-M-kaken 2004-134p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/46856/files/SC-PR-SEGI-M-kaken 2004-134p.pdf"},"version_id":"8173b319-8e46-4fcc-bf63-4edd8735918f"}]},"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":"金属及びヘテロ元素の反応特性を複合的に活用した効率的分子変換反応の開発","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"金属及びヘテロ元素の反応特性を複合的に活用した効率的分子変換反応の開発"},{"subitem_title":"Development of Efficient Molecular Transformations Using Metal and Heteroatom Compounds","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2830"],"pubdate":{"attribute_name":"公開日","attribute_value":"2019-02-14"},"publish_date":"2019-02-14","publish_status":"0","recid":"46856","relation_version_is_last":true,"title":["金属及びヘテロ元素の反応特性を複合的に活用した効率的分子変換反応の開発"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T14:36:57.959208+00:00"}