{"created":"2021-03-01T06:32:50.698479+00:00","id":24857,"links":{},"metadata":{"_buckets":{"deposit":"0330198d-f8c7-4870-8e51-7a90dba44ba8"},"_deposit":{"id":"24857","owners":[],"pid":{"revision_id":0,"type":"depid","value":"24857"},"status":"published"},"_oai":{"id":"oai:nagoya.repo.nii.ac.jp:00024857","sets":["1903:1904:1905"]},"author_link":["73939","73940","73941","73942"],"item_10_biblio_info_6":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2017-08-04","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"15","bibliographicPageEnd":"7973","bibliographicPageStart":"7964","bibliographicVolumeNumber":"82","bibliographic_titles":[{"bibliographic_title":"Journal of Organic Chemistry","bibliographic_titleLang":"en"}]}]},"item_10_description_4":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"Cycloaddition reactions of 1,6-diynes bearing methyl terminal groups with p-anisaldehyde were conducted using a cationic ruthenium catalyst with a η^5 -pentamethylcyclopentadienyl ligand in THF at room temperature to afford dienyl ketones via ring opening of the initially formed fused pyrans. (Z)-Stereoisomers of dienyl ketones were selectively obtained using the ruthenium catalyst, whereas previously reported rhodium catalysts produced (E)-isomers. These (E)- and (Z)-selectivities are kinetically controlled as the control experiments showed that the E/Z-isomerization of (E)-dienylketone occurs at 70 °C for 10 h to afford an E/Z-ratio of almost 1:1. The origin of this characteristic stereoselectivity for the ruthenium catalyst was attributed to the direct ring opening of the CpRu^+ -coordinated pyran complex intermediates on the basis of theoretical calculations [PCM (THF) M06L/SDD-6-311++G(d,p)//B3LYP/LanL2DZ-6-31G(d)] and control experiments. The (Z)-selectivity increased when the bulkiness of the diyne terminal substituents increased. Notably, the reaction of 1,6-diynes bearing tert-butyl terminal groups with various α,β-unsaturated aldehydes exclusively afforded (Z)-dienyl ketones even at 70 °C when a cationic ruthenium complex with a smaller η^5 -cyclopentadienyl (Cp) ligand was used as the catalyst. The same Cp complex was found to be also efficient for the hydrocarbamoylative cyclization of sterically demanding 1,6-diynes bearing tertiary or quaternary carbon tethers with N,N-dimethylformamide.","subitem_description_language":"en","subitem_description_type":"Abstract"}]},"item_10_identifier_60":{"attribute_name":"URI","attribute_value_mlt":[{"subitem_identifier_type":"DOI","subitem_identifier_uri":"http://doi.org/10.1021/acs.joc.7b01229"},{"subitem_identifier_type":"HDL","subitem_identifier_uri":"http://hdl.handle.net/2237/27077"}]},"item_10_publisher_32":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"ACS Publications","subitem_publisher_language":"en"}]},"item_10_relation_11":{"attribute_name":"DOI","attribute_value_mlt":[{"subitem_relation_type":"isVersionOf","subitem_relation_type_id":{"subitem_relation_type_id_text":"https://doi.org/10.1021/acs.joc.7b01229","subitem_relation_type_select":"DOI"}}]},"item_10_rights_12":{"attribute_name":"権利","attribute_value_mlt":[{"subitem_rights":"“This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Journal of Organic Chemistry], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [ http://pubs.acs.org/articlesonrequest/AOR-gsXP3SHHURzcsmdS3cwp].”","subitem_rights_language":"en"}]},"item_10_select_15":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_select_item":"author"}]},"item_10_source_id_7":{"attribute_name":"ISSN","attribute_value_mlt":[{"subitem_source_identifier":"0022-3263","subitem_source_identifier_type":"PISSN"}]},"item_1615787544753":{"attribute_name":"出版タイプ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_ab4af688f83e57aa","subitem_version_type":"AM"}]},"item_access_right":{"attribute_name":"アクセス権","attribute_value_mlt":[{"subitem_access_right":"open access","subitem_access_right_uri":"http://purl.org/coar/access_right/c_abf2"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"Yoshihiko, Yamamoto","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"73939","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"Yuta, Okude","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"73940","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"Shota, Mori","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"73941","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"Masatoshi, Shibuya","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"73942","nameIdentifierScheme":"WEKO"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2018-08-04"}],"displaytype":"detail","filename":"JOC_MS_rev.pdf","filesize":[{"value":"895.1 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"JOC_MS_rev.pdf ファイル公開日:2018/08/04","objectType":"fulltext","url":"https://nagoya.repo.nii.ac.jp/record/24857/files/JOC_MS_rev.pdf"},"version_id":"39f7154e-2d01-4970-a6a4-754faf28df69"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"journal article","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"Combined Experimental and Computational Study on Ruthenium(II)-Catalyzed Reactions of Diynes with Aldehydes and N,N‑Dimethylformamide","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Combined Experimental and Computational Study on Ruthenium(II)-Catalyzed Reactions of Diynes with Aldehydes and N,N‑Dimethylformamide","subitem_title_language":"en"}]},"item_type_id":"10","owner":"1","path":["1905"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2017-11-08"},"publish_date":"2017-11-08","publish_status":"0","recid":"24857","relation_version_is_last":true,"title":["Combined Experimental and Computational Study on Ruthenium(II)-Catalyzed Reactions of Diynes with Aldehydes and N,N‑Dimethylformamide"],"weko_creator_id":"1","weko_shared_id":-1},"updated":"2023-01-16T04:15:22.034940+00:00"}