{"created":"2023-07-27T07:00:18.445814+00:00","id":60182,"links":{},"metadata":{"_buckets":{"deposit":"13d3f017-0f08-45ca-b7c5-071c6456bbd8"},"_deposit":{"created_by":18,"id":"60182","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"60182"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00060182","sets":["2812:2813:2838"]},"author_link":["26369","81412"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1997-03-03","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"2p.","bibliographicVolumeNumber":"1994 – 1995","bibliographic_titles":[{"bibliographic_title":"平成7(1995)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":"1995 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":"Ohba, Masashi"}],"nameIdentifiers":[{"nameIdentifier":"26369","nameIdentifierScheme":"WEKO"},{"nameIdentifier":"60115219","nameIdentifierScheme":"e-Rad","nameIdentifierURI":"https://kaken.nii.ac.jp/ja/search/?qm=60115219"},{"nameIdentifier":"60115219","nameIdentifierScheme":"研究者番号","nameIdentifierURI":"https://nrid.nii.ac.jp/nrid/1000060115219"}]}]},"item_9_description_21":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"ヒトデDermasterias imbricataより単離された含硫ベンジルイソキノリン型アルカロイドimbricatine(1)を合成し,その構造と絶対配置を決定することを目的として以下の研究を行った.\n1.N,N-Diethyl-3,5-dimethoxybenzamideをリチウム化後硫黄で処理し,更に4-methoxybenzyl chlorideにてS-アルキル化した.次にLiAlH_4還元後,ClCO_2Etにてクロリド体へと変換した.これにSchollkopfの不斉アミノ酸合成法を適用し,光学活性含硫D-フェニルアラニン誘導体2を好収率で得た.\n2.2を4-methoxyphenylacetyl chlorideにてアミド体へと変換後,trimethylsilyl polyphoshateでBischler-Napieralski閉環し更に-78℃にてNaBH_4還元して1,3-cis-ベンジルテトラヒドロイソキノリン体3を得た.\n3.予想される3位でのエピメリ化を避ける目的で3のエステル部をLiAlH_4還元後,オキサゾロン体へと変換した.つづいてS上の保護基を除去するためトリフルオロ酢酸第二水銀で処理し,1の南半球をチオール体4として得ることに成功した.\n4.4に我々の開発した5-arylthio-3-methyl-L-histidine類の一般的合成法を適用し1の北半球を構成する3-methyl-L-histidine部を構築した.つづいてオキサゾロン環の開裂後,両アミノ基をBoc基で保護し,Swern酸化,MeOH中でのI_2酸化を経てエステル体5へと導き,ここに1の全骨格を有する化合物5の合成に成功した.\n5.5の保有する全ての保護基を除去する条件を(±)-1-(4-methoxybenzyl)-6,8-dimethoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid methyl esterのN-Boc体6にて検討した.その結果,6を過剰のBBr_3にて処理する方法により全ての保護基を除去できることが判明し,合わせて水溶性生成物の単離方法にも若干の知見を得ることができた.今後,この条件を5に適用して1の合成を検討すると共に,本研究目的の達成を目指す予定である.","subitem_description_type":"Abstract"},{"subitem_description":"With a view to confirming the structure and absolute configuration of imbricatine (1), a benzyltetrahydroisoquinoline alkaloid, isolated from the starfish Dermasterias imbricata, we have undertaken the chiral synthesis of the candidate structure 1.\n1. Lithiation of N,N-diethyl-3,5-dimethoxybenzamide followed by successive treatment with elemental sulfur and 4-methoxybenzyl chloride provided the sulfide, which was then converted to the chloride 2 via reduction with LiAlH_4 and chlorination with ClCO_2Et. On application of asymmetric synthesis of alpha-amino acid developed by Schollkopf, 2 afforded the sulfur-containing D-phenylalanine derivative 3 in good yield.\n2. Schotten-Baumann reaction of 3 with 4-methoxyphenylacetyl chloride furnished the amide, which was subjected to Bischler-Napieralski cyclization with trimethylsily polyphosphate followed by reduction with NaBH_4 at-78ﾟC,giving the 1,3-cis-benzyltetrahydroisoquinoline derivative 4.\n3. In order to avoid epimerization of 4 at the 3-position, the ester group of 4 was reduced with LiAlH_4 to give the amino alcohol 5. After conversion of 5 into the oxazolone 6, deprotection of 4-methoxybenzyl group of 6 was performed with (CF_3CO_2)_2Hg followed by NaBH_4 treatment, providing the southern hemisphere of 1 as the thiol 7.\n4. Application of our general synthetic route for 5-arylthio-3-methyl-L-histidines to 7 led to the construction of 3-methyl-L-histidine portion (the northern hemisphere of 1). The histidine derivative 8 was then transformed to the ester 9 via hydrolysis of the oxazole ring of 8, protection of two amino groups, Swern oxidation, and alkaline iodine oxidation in MeOH.Thus, we have achieved the synthesis of the penultimate ester 9 possessing the parent framework of 1.\nDeprotection of 9 leading to 1 is currently under way.","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:06672097, 研究期間(年度):1994 – 1995","subitem_description_type":"Other"},{"subitem_description":"出典：研究課題「海洋生物由来含硫アルカロイドImbricatineの合成研究」課題番号06672097\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-06672097/066720971995kenkyu_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":"金沢大学薬学部","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00066433","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=60115219"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/search/?qm=60115219","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-06672097/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-06672097/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-06672097/066720971995kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-06672097/066720971995kenkyu_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":"大場, 正志"}],"nameIdentifiers":[{"nameIdentifier":"81412","nameIdentifierScheme":"WEKO"},{"nameIdentifier":"60115219","nameIdentifierScheme":"e-Rad","nameIdentifierURI":"https://kaken.nii.ac.jp/ja/search/?qm=60115219"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2022-06-17"}],"displaytype":"detail","filename":"PH-PR-OHBA-M-kaken 1997-2p.pdf","filesize":[{"value":"80.7 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"PH-PR-OHBA-M-kaken 1997-2p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/60182/files/PH-PR-OHBA-M-kaken 1997-2p.pdf"},"version_id":"8df46468-0c49-4a3b-9218-04ea407f50b6"}]},"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":"海洋生物由来含硫アルカロイドImbricatineの合成研究","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"海洋生物由来含硫アルカロイドImbricatineの合成研究"},{"subitem_title":"Synthetic Studies on Imbricatine, a Sulfur-containing Benzyltetrahydroisoquinoline Alkaloid from the Starfish Dermasterias imbricata.","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2838"],"pubdate":{"attribute_name":"公開日","attribute_value":"2022-06-17"},"publish_date":"2022-06-17","publish_status":"0","recid":"60182","relation_version_is_last":true,"title":["海洋生物由来含硫アルカロイドImbricatineの合成研究"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2024-07-01T06:39:56.491277+00:00"}