{"created":"2024-10-24T02:06:31.832249+00:00","id":2000531,"links":{},"metadata":{"_buckets":{"deposit":"22618456-cd84-4e47-b332-33bffd25cddd"},"_deposit":{"created_by":29,"id":"2000531","owners":[29],"pid":{"revision_id":0,"type":"depid","value":"2000531"},"status":"published"},"_oai":{"id":"oai:ir.kagoshima-u.ac.jp:02000531","sets":["35:67"]},"author_link":["144317","144316","144323","144320","10999"],"control_number":"2000531","item_6_biblio_info_5":{"attribute_name":"bibliographic_information","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2007-12-15","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"5","bibliographicPageEnd":"294","bibliographicPageStart":"283","bibliographicVolumeNumber":"6","bibliographic_titles":[{"bibliographic_title":"Journal of Computer Chemistry, Japan","bibliographic_titleLang":"en"}]}]},"item_6_date_6":{"attribute_name":"作成日","attribute_value_mlt":[{"subitem_date_issued_datetime":"2007-12-15","subitem_date_issued_type":"Issued"}]},"item_6_description_4":{"attribute_name":"要約(Abstract)","attribute_value_mlt":[{"subitem_description":"共役ジエノン環系の2-ピリドン (1) が示す、フロンティア分子軌道（FMO）法で判断できにくい多様な光付加環化反応性（励起種、ぺリ、位置、配向、立体選択性等）の原因を、主にMOPAC2002-PM5法を用いた全反応過程の遷移状態（TS1、TS2、TS3等）解析シミュレーションにより明らかにした。\n直接光照射による励起一重項 1sからのanti-3,6-ht（head-to-tail）[4+4]二量体 (3) の生成は、FMOでは説明できない。この反応は励起二量体（Excimer）を経由し、第一遷移状態（TS1）のエネルギーが選択性を支配しており、その構造（r3-6=2.14Åなど）は四中心協奏反応的と推定された。静電相互作用と軌道相互作用の競合が示唆される。1sとアクリル酸エステル (2) などとの光交叉付加の主付加物（endo-3,4-ht[2+2]付加体：4) などの生成も、励起錯体（Exciplex）を経由し、TS1エネルギー支配で、四中心協奏反応的である。新規な付加による八員環アゾシノン体 (5) の生成では、励起ビラジカル関与の過程（TS4）が示唆された。光増感反応で生じる 1の三重項 1tと 2などとの主付加物（exo-5,6-hh（head-to-head）[2+2]付加体：7) などは、二中心的ねじれ配座のTS1が選択性を支配し、ねじれ配座のビラジカルを経て、TS2（閉環）のエネルギーがTS3（解離）より低いことで生成していると判断された。\n以上のように選択性の決定される反応段階や遷移状態の構造とエネルギーを推定した。","subitem_description_language":"ja","subitem_description_type":"Other"},{"subitem_description":"A Frontier Molecular Orbital (FMO) analysis is not so effective for the singlet peri-, site-, regio- and stereoselectivities of singlet photodimerization (anti-3,6-[4+4] cycloaddition for 3) of 2-pyridone (1) and for the cross additions (mainly endo-3,4-ht-[2+2] cycloaddition for 4) with acrylates (2). Their Origins were analysed by transition state (TS) analysis of whole reaction (TS1, TS2, TS3) using MOPAC-PM5 and UCIS/6-31+G(d)//PM5 levels of calculation, and the major factors of the selectivities were inferred quantitatively. The singlet reactions may be concerted, controlled by TS1, and may be competed by orbital overlapping and ionic factors. The Origin for a novel adduct, azocinone (5) between excited singlet 1 and 2 was also estimated by PM5 simulation. The triplet and regioselective cross additions (mainly exo-5,6-hh-[2+2] cycloaddition for 7) between 1 and 2 were inferred to be two-step reactions, and to pass through twisted biradicals, with the first-step transition TS1 energy smaller than the second-step one. The energy of TS2 (ring- closure) was lower than that of TS3 (bond- cleavage).","subitem_description_language":"en","subitem_description_type":"Other"}]},"item_6_publisher_23":{"attribute_name":"公開者・出版者","attribute_value_mlt":[{"subitem_publisher":"日本コンピュータ化学会","subitem_publisher_language":"ja"}]},"item_6_relation_11":{"attribute_name":"item_6_relation_11","attribute_value_mlt":[{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://doi.org/10.2477/jccj.6.283","subitem_relation_type_select":"DOI"}}]},"item_6_rights_12":{"attribute_name":"権利","attribute_value_mlt":[{"subitem_rights":"(c) 2007 Society of Computer Chemistry, Japan","subitem_rights_language":"en"}]},"item_6_source_id_7":{"attribute_name":"item_6_source_id_7","attribute_value_mlt":[{"subitem_source_identifier":"13473824","subitem_source_identifier_type":"EISSN"}]},"item_6_source_id_9":{"attribute_name":"item_6_source_id_9","attribute_value_mlt":[{"subitem_source_identifier":"AA11657986","subitem_source_identifier_type":"NCID"}]},"item_6_version_type_14":{"attribute_name":"出版タイプ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_970fb48d4fbd8a85","subitem_version_type":"VoR"}]},"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":"徳永, 大輔","creatorNameLang":"ja"},{"creatorName":"Tokunaga, Daisuke","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"144317","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"下茂, 徹朗","creatorNameLang":"ja"},{"creatorName":"Shimo, Tetsuro","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"144316","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"橋本, 浩晃","creatorNameLang":"ja"},{"creatorName":"Hashimoto, Hiroaki","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"144323","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"大戸, 朋子","creatorNameLang":"ja"},{"creatorName":"Ooto, Tomoko","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"144320","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"染川, 賢一","creatorNameLang":"ja"},{"creatorName":"Somekawa, Kenichi","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"10999","nameIdentifierScheme":"WEKO"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_access","date":[{"dateType":"Available","dateValue":"2024-10-24"}],"displaytype":"detail","filename":"6_283.pdf","filesize":[{"value":"475.8 KB"}],"format":"application/pdf","mimetype":"application/pdf","url":{"label":"6_283","objectType":"fulltext","url":"https://ir.kagoshima-u.ac.jp/record/2000531/files/6_283.pdf"},"version_id":"484966a6-98b7-438b-b261-715104aae817"}]},"item_keyword":{"attribute_name":"キーワード","attribute_value_mlt":[{"subitem_subject":"光付加環化反応","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"2-ピリドン","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"位置・配向選択性","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"遷移状態解析","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"PM5","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"非制限励起配置（UCIS）","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"Photocycloaddition reaction","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"2-Pyridone","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"Site-and regioselectivities","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"Transition state analysis","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"UCIS","subitem_subject_language":"en","subitem_subject_scheme":"Other"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"jpn"}]},"item_resource_type":{"attribute_name":"item_resource_type","attribute_value_mlt":[{"resourcetype":"journal article","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"分子軌道法を用いた2-ピリドンの光付加環化選択性の原因解析","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"分子軌道法を用いた2-ピリドンの光付加環化選択性の原因解析","subitem_title_language":"ja"},{"subitem_title":"MO Analysis of Origin in Some Selective Photocycloadditions of 2-Pyridones","subitem_title_language":"en"}]},"item_type_id":"6","owner":"29","path":["67"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2024-10-24"},"publish_date":"2024-10-24","publish_status":"0","recid":"2000531","relation_version_is_last":true,"title":["分子軌道法を用いた2-ピリドンの光付加環化選択性の原因解析"],"weko_creator_id":"29","weko_shared_id":-1},"updated":"2024-10-24T02:55:54.055937+00:00"}