{"created":"2023-06-19T10:30:13.927939+00:00","id":10455,"links":{},"metadata":{"_buckets":{"deposit":"9a0090a9-56f6-4fa9-9748-14d07838cb8a"},"_deposit":{"created_by":18,"id":"10455","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"10455"},"status":"published"},"_oai":{"id":"oai:muroran-it.repo.nii.ac.jp:00010455","sets":["41:227"]},"author_link":["58518"],"control_number":"10455","item_81_date_granted_17":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"2021-03-23"}]},"item_81_degree_grantor_10":{"attribute_name":"学位授与機関","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_language":"ja","subitem_degreegrantor_name":"室蘭工業大学"},{"subitem_degreegrantor_language":"en","subitem_degreegrantor_name":"Muroran Institute of Technology"}],"subitem_degreegrantor_identifier":[{"subitem_degreegrantor_identifier_name":"10103","subitem_degreegrantor_identifier_scheme":"kakenhi"}]}]},"item_81_degree_name_11":{"attribute_name":"学位名","attribute_value_mlt":[{"subitem_degreename":"博士（工学）","subitem_degreename_language":"ja"}]},"item_81_description_25":{"attribute_name":"フォーマット","attribute_value_mlt":[{"subitem_description":"application/pdf","subitem_description_type":"Other"}]},"item_81_description_7":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"医薬品を含む多くの生物活性化合物は光学活性物質であり, その鏡像異性体は異なる生体内活性を示すことが多いため, 有効な一方の鏡像異性体を高立体選択的に合成するための不斉合成反応，特に不斉触媒を用いる触媒的不斉合成反応の開発は創薬分野や様々な光学活性機能性分子を創製するために重要である.その不斉触媒の中で，金属を含有しない有機分子触媒は空気中で安定であり取り扱いやすく安価であるという利点などを有するため, 次世代の環境調和型触媒として現在活発な研究開発が行なわれている.著者は, 新規多点認識型有機分子触媒としてこれまでその機能性の検討がなされていなかった糖型γ—アミノアアルコールとγ—アミノエーテルに着目し，その不斉触媒としての機能解明を不斉マイケル付加反応に適用することにより試みた. 適用する不斉マイケル付加反応は炭素—炭素結合形成反応として，さらに四級不斉中心の構築にも有用であることから各種医薬品や複雑な生物活性化合物を合成するための鍵反応として汎用されている。新規有機分子触媒として糖型γ—アミノアアルコールおよびγ—アミノエーテル有機分子触媒を容易に入手可能なキシロースから数工程を経て創製し, γ—アミノアアルコールおよびγ—アミノエーテル触媒の不斉触媒活性をß-ケトエステル類とニトロスチレン類との不斉マイケル付加反応に適用し検討した．その結果として, γ—アミノアアルコールおよびγ—アミノエーテル触媒が本反応において不斉触媒活性を示し，優れた化学収率と良好な光学収率で光学活性マイケル付加生成物を与えることを見出した. 得られた生成物は，創薬のための様々な生物活性化合物の合成中間体として有用であり，この合成中間体から新薬候補化合物を創製できることが期待される．本研究において著者は，「その分子中に基質との共有結合部位と水素結合部位，さらには反応のエナンチオ選択性の制御に有効な糖構造部位を併せもつ新規多点認識機能を発現する糖型γ—アミノアルコールおよびγ—アミノエーテル有機分子触媒」を開発することに成功し, それらが創薬に有効な不斉マイケル付加反応において良好な不斉触媒活性を示すことを明らかにした. 開発した本糖型触媒は，他の有用な不斉触媒反応においても触媒機能を示すことが期待され，さらに，本反応によって得られる化合物は様々な医薬品をはじめとする生物活性化合物の合成中間体として有用であることから，本研究の成果は, 新薬創製を指向した合成開発研究に大きく貢献できると期待される.","subitem_description_language":"ja","subitem_description_type":"Abstract"},{"subitem_description":"A lot of biologically active compounds, including drugs, are optically active and often only one of the enantiomer shows a high biologically activity. Therefore, it is important to develop a synthetic methodology for providing only necessary enantiomer. As the methodology, catalytic asymmetric synthesis, in which the use of a low amount of a chiral catalyst theoretically enables infinite production of optically active compounds, is the most efficient in the synthetic organic chemistry field. Moreover, this methodology is also important in terms of energy saving and environmental friendliness. The chiral catalysts used in catalytic asymmetric syntheses can be divided into two categories of organometallic catalyst and metal-free organocatalyst. Particularly, organocatalyst is stable in air, nontoxic, easy to handle, and inexpensive, so they are being focused on as next-generation, environmentally friendly catalysts. Author focused γ-amino alcohol as an organocatalyst. In contrast to β-amino alcohol as an organocatalyst, the utility of γ-amino alcohol was not much explored even though it is expected to have a high potential functionality as an organocatalyst similar to β-amino alcohol. As a compound, author selected a sugar based γ-amino alcohol and its derivative fixing 1,2-O-isopropylidene-D-xylofuranose structure as a backbone. This catalyst is expected to work as multipoint recognition catalyst having basic site, covalent and non-covalent hydrogen bonding sites in the single molecule. Proposed γ-amino alcohol contains an amino group acting as basic or covalent site and hydroxyl group acting as a non-covalent hydrogen bonding site and also sugar backbone acting as steric influence site for controlling stereoselective reaction course. Furthermore, this γ-amino alcohol can be easily prepared from commercially available D-xylose by few steps. As a reaction for providing the utility of the γ-amino alcohol, asymmetric Michael addition of β-keto esters with nitroolefins was selected. The Michael adducts from this reaction contain both quaternary and tertiary chiral carbon centers in the structure and the adducts work as an important synthetic precursor of the synthesis of many biologically active compounds including pharmaceuticals such as platencin (antibiotic). Author tried this reaction of β-keto esters with nitroolefins using sugar based γ-amino alcohol and γ-amino silyl ether organocatalysts at first time. As a result, the both catalysts were showed good catalytic activity in this reaction and the desired chiral Michael adducts was obtained in good chemical yields, diastereoselectivities and enantioselectivities. In this study, author revealed that the new explored sugar type γ-amino organocatalyst showed satisfactory catalytic activities in the Michael addition. It is expected that these results should be able to greatly contribute the development of new drug and its related compounds.","subitem_description_language":"en","subitem_description_type":"Abstract"}]},"item_81_dissertation_number_13":{"attribute_name":"学位授与番号","attribute_value_mlt":[{"subitem_dissertationnumber":"甲第469号"}]},"item_81_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.15118/00010394","subitem_identifier_reg_type":"JaLC"}]},"item_81_subject_9":{"attribute_name":"日本十進分類法","attribute_value_mlt":[{"subitem_subject":"499","subitem_subject_scheme":"NDC"}]},"item_81_text_12":{"attribute_name":"学位の種別","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"課程博士"}]},"item_81_text_14":{"attribute_name":"報告番号","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"甲第469号"}]},"item_81_text_15":{"attribute_name":"学位記番号","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"博甲第469号"}]},"item_81_text_16":{"attribute_name":"研究科・専攻","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"工学専攻"}]},"item_81_version_type_24":{"attribute_name":"著者版フラグ","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":[{"creatorAffiliations":[{"affiliationNameIdentifiers":[],"affiliationNames":[{"affiliationName":""}]}],"creatorNames":[{"creatorName":"DIVAKAR, Ganesan","creatorNameLang":"en"},{"creatorName":"ディバカル, ガネサン","creatorNameLang":"ja"}],"familyNames":[{},{}],"givenNames":[{},{}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2021-06-23"}],"displaytype":"detail","filename":"A469_summary.pdf","filesize":[{"value":"243.0 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"A469_summary","objectType":"abstract","url":"https://muroran-it.repo.nii.ac.jp/record/10455/files/A469_summary.pdf"},"version_id":"5a177307-4e28-4aa3-be87-cbf28b087195"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2022-03-23"}],"displaytype":"detail","filename":"A469.pdf","filesize":[{"value":"3.8 MB"}],"format":"application/pdf","mimetype":"application/pdf","url":{"label":"A469","objectType":"fulltext","url":"https://muroran-it.repo.nii.ac.jp/record/10455/files/A469.pdf"},"version_id":"f4d37a82-d2a0-4565-994b-ab1fef094d74"}]},"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":"doctoral thesis","resourceuri":"http://purl.org/coar/resource_type/c_db06"}]},"item_title":"Development of Sugar Based γ-Amino Organocatalyst for Asymmetric Michael Addition","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Development of Sugar Based γ-Amino Organocatalyst for Asymmetric Michael Addition","subitem_title_language":"en"},{"subitem_title":"不斉マイケル付加反応に用いる糖型 γ-アミノ有機分子触媒の開発","subitem_title_language":"ja"}]},"item_type_id":"81","owner":"18","path":["227"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2021-06-23"},"publish_date":"2021-06-23","publish_status":"0","recid":"10455","relation_version_is_last":true,"title":["Development of Sugar Based γ-Amino Organocatalyst for Asymmetric Michael Addition"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2024-01-22T02:01:37.840043+00:00"}