WEKO3
アイテム
{"_buckets": {"deposit": "1dff66cd-2bf3-4bb1-8eed-30a4e1fcfed5"}, "_deposit": {"created_by": 15, "id": "10276", "owners": [15], "pid": {"revision_id": 0, "type": "depid", "value": "10276"}, "status": "published"}, "_oai": {"id": "oai:sucra.repo.nii.ac.jp:00010276", "sets": ["502"]}, "author_link": ["17561"], "item_113_alternative_title_1": {"attribute_name": "タイトル(別言語)", "attribute_value_mlt": [{"subitem_alternative_title": "光学活性1,3-アミノアルコールの不斉アルキル化、アリール化反応への応用と置換基によるキラリティーの制御"}]}, "item_113_biblio_info_9": {"attribute_name": "書誌情報", "attribute_value_mlt": [{"bibliographicIssueDates": {"bibliographicIssueDate": "2010", "bibliographicIssueDateType": "Issued"}, "bibliographicPageEnd": "64", "bibliographicPageStart": "1"}]}, "item_113_date_35": {"attribute_name": "作成日", "attribute_value_mlt": [{"subitem_date_issued_datetime": "2010-03-10", "subitem_date_issued_type": "Created"}]}, "item_113_description_23": {"attribute_name": "抄録", "attribute_value_mlt": [{"subitem_description": "This thesis reports the application of novel optically active 1,3-amino alcohols to catalytic asymmetric reactions and the substituent effect on the chirality control.\nA series of novel optically active 1,3-amino alcohols have been synthesized from commercially available cis-(1R,2S)-2-benzamidocyclohexanecarboxylic acid, and showed moderate to good enantioselectivities in asymmetric addition of diethylzinc to aromatic aldehydes. Most interestingly, both enantiomers of a given product were obtained using the ligands with the same chirality. The results clearly showed that not only the enantioselectivity but also the stereochemistry of the product was controlled by the N-substituents and the substituents on the vicinity carbon to hydroxyl group; (1R,2S)-2-pyrrolidin-1’-ylcyclohexylmethanol showed the best promoting ability to aromatic aldehydes with ®-selectivity (79.4% ee) in the chiral 1,3-amino alcohols studied. On the other hand (1R,2S)-2-benzylaminocyclohexyl(diphenyl)methanol showed the opposite (S)-selectivity (66.0% ee).\nThe optically active 1,3-amino alcohols have been also shown to catalyze the asymmetric arylation of aryl aldehydes using boronic acids as the source of transferable aryl groups, with good yields and moderate to high enantioselectivities (up to \u003e99% ee). The results demonstrated that the substituents to the vicinity of hydroxyl group have a crucial effect on chirality control. The substituent effect of 1,3-amino alcohols was confirmed for all the aromatic aldehydes studied. Both enantiomers of a product could be obtained by using the ligands with the same chirality. In addition, a good linear correlation was observed between the enantioselectivity and the electronic propertiy of the substituents on a substrate (The stronger electron-withdrawing substituents on the para-position exhibited higher enantiomeric excess, while the stronger electron-donation substituents on the para-position showed lower selectivity).", "subitem_description_type": "Abstract"}]}, "item_113_description_25": {"attribute_name": "注記", "attribute_value_mlt": [{"subitem_description": "指導教員: 埼玉大学大学院理工学研究科教授 廣瀬卓司", "subitem_description_type": "Other"}]}, "item_113_description_33": {"attribute_name": "資源タイプ", "attribute_value_mlt": [{"subitem_description": "text", "subitem_description_type": "Other"}]}, "item_113_description_34": {"attribute_name": "フォーマット", "attribute_value_mlt": [{"subitem_description": "application/pdf", "subitem_description_type": "Other"}]}, "item_113_record_name_8": {"attribute_name": "書誌", "attribute_value_mlt": [{"subitem_record_name": "博士論文(埼玉大学大学院理工学研究科(博士後期課程))"}]}, "item_113_text_3": {"attribute_name": "著者 ローマ字", "attribute_value_mlt": [{"subitem_text_value": "Wang, Xiang-Bo"}]}, "item_113_text_36": {"attribute_name": "アイテムID", "attribute_value_mlt": [{"subitem_text_value": "GD0000147"}]}, "item_113_text_39": {"attribute_name": "公開日(XooNIps)", "attribute_value_mlt": [{"subitem_text_value": "Mar 10, 2010 09:09:18"}]}, "item_113_text_4": {"attribute_name": "著者 所属", "attribute_value_mlt": [{"subitem_text_value": "埼玉大学大学院理工学研究科 (博士後期課程)理工学専攻"}]}, "item_113_text_40": {"attribute_name": "最終更新日(XooNIps)", "attribute_value_mlt": [{"subitem_text_value": "Mar 10, 2010 16:36:50"}]}, "item_113_text_41": {"attribute_name": "更新履歴(XooNIps)", "attribute_value_mlt": [{"subitem_text_value": "Mar 10, 2010 フリーキーワード, インデックス, 抄録 を変更"}]}, "item_113_text_42": {"attribute_name": "登録者(XooNIps)", "attribute_value_mlt": [{"subitem_text_value": "sucra_jim4"}]}, "item_113_text_43": {"attribute_name": "閲覧数(XooNIps)", "attribute_value_mlt": [{"subitem_text_value": "1143"}]}, "item_113_text_44": {"attribute_name": "ダウンロード数(XooNIps)", "attribute_value_mlt": [{"subitem_text_value": "2405"}]}, "item_113_text_45": {"attribute_name": "XooNIps_ITEM_KEY", "attribute_value_mlt": [{"subitem_text_value": "12018"}]}, "item_113_text_5": {"attribute_name": "著者 所属(別言語)", "attribute_value_mlt": [{"subitem_text_value": "Graduate School of Science and Engineering, Saitama University"}]}, "item_creator": {"attribute_name": "著者", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "王, 祥波", "creatorNameLang": "ja"}], "nameIdentifiers": [{"nameIdentifier": "17561", "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": "2018-01-23"}], "displaytype": "detail", "download_preview_message": "", "file_order": 0, "filename": "GD0000147.pdf", "filesize": [{"value": "663.9 kB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_note", "mimetype": "application/pdf", "size": 663900.0, "url": {"label": "GD0000147.pdf", "url": "https://sucra.repo.nii.ac.jp/record/10276/files/GD0000147.pdf"}, "version_id": "0d76ef37-604b-4e6a-85ec-5bf68ad29807"}]}, "item_keyword": {"attribute_name": "キーワード", "attribute_value_mlt": [{"subitem_subject": "chirality control", "subitem_subject_scheme": "Other"}, {"subitem_subject": "asymmetric alkylation", "subitem_subject_scheme": "Other"}, {"subitem_subject": "asymmetric arylation", "subitem_subject_scheme": "Other"}, {"subitem_subject": "1,3-amino alcohols", "subitem_subject_scheme": "Other"}, {"subitem_subject": "cis-(1R,2S)-2-benzamidocyclohexanecarboxylic acid", "subitem_subject_scheme": "Other"}, {"subitem_subject": "aromatic aldehyde", "subitem_subject_scheme": "Other"}]}, "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": "thesis", "resourceuri": "http://purl.org/coar/resource_type/c_46ec"}]}, "item_title": "Application of chiral 1,3-amino alcohols to asymmetric alkylation and arylation and the substituent effect on chirality control", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "Application of chiral 1,3-amino alcohols to asymmetric alkylation and arylation and the substituent effect on chirality control", "subitem_title_language": "en"}]}, "item_type_id": "113", "owner": "15", "path": ["502"], "permalink_uri": "https://sucra.repo.nii.ac.jp/records/10276", "pubdate": {"attribute_name": "PubDate", "attribute_value": "2010-03-10"}, "publish_date": "2010-03-10", "publish_status": "0", "recid": "10276", "relation": {}, "relation_version_is_last": true, "title": ["Application of chiral 1,3-amino alcohols to asymmetric alkylation and arylation and the substituent effect on chirality control"], "weko_shared_id": -1}
Application of chiral 1,3-amino alcohols to asymmetric alkylation and arylation and the substituent effect on chirality control
https://sucra.repo.nii.ac.jp/records/10276
https://sucra.repo.nii.ac.jp/records/10276e23d7a1f-6a38-433b-86a7-63895cbe249c
名前 / ファイル | ライセンス | アクション |
---|---|---|
GD0000147.pdf (663.9 kB)
|
|
Item type | 学位論文 / Thesis or Dissertation(1) | |||||
---|---|---|---|---|---|---|
公開日 | 2010-03-10 | |||||
タイトル | ||||||
言語 | en | |||||
タイトル | Application of chiral 1,3-amino alcohols to asymmetric alkylation and arylation and the substituent effect on chirality control | |||||
言語 | ||||||
言語 | eng | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | chirality control | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | asymmetric alkylation | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | asymmetric arylation | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | 1,3-amino alcohols | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | cis-(1R,2S)-2-benzamidocyclohexanecarboxylic acid | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | aromatic aldehyde | |||||
資源タイプ | ||||||
資源タイプ識別子 | http://purl.org/coar/resource_type/c_46ec | |||||
資源タイプ | thesis | |||||
タイトル(別言語) | ||||||
その他のタイトル | 光学活性1,3-アミノアルコールの不斉アルキル化、アリール化反応への応用と置換基によるキラリティーの制御 | |||||
著者 |
王, 祥波
× 王, 祥波 |
|||||
著者 ローマ字 | ||||||
Wang, Xiang-Bo | ||||||
著者 所属 | ||||||
埼玉大学大学院理工学研究科 (博士後期課程)理工学専攻 | ||||||
著者 所属(別言語) | ||||||
Graduate School of Science and Engineering, Saitama University | ||||||
書誌 | ||||||
収録物名 | 博士論文(埼玉大学大学院理工学研究科(博士後期課程)) | |||||
書誌情報 |
p. 1-64, 発行日 2010 |
|||||
抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | This thesis reports the application of novel optically active 1,3-amino alcohols to catalytic asymmetric reactions and the substituent effect on the chirality control. A series of novel optically active 1,3-amino alcohols have been synthesized from commercially available cis-(1R,2S)-2-benzamidocyclohexanecarboxylic acid, and showed moderate to good enantioselectivities in asymmetric addition of diethylzinc to aromatic aldehydes. Most interestingly, both enantiomers of a given product were obtained using the ligands with the same chirality. The results clearly showed that not only the enantioselectivity but also the stereochemistry of the product was controlled by the N-substituents and the substituents on the vicinity carbon to hydroxyl group; (1R,2S)-2-pyrrolidin-1’-ylcyclohexylmethanol showed the best promoting ability to aromatic aldehydes with ®-selectivity (79.4% ee) in the chiral 1,3-amino alcohols studied. On the other hand (1R,2S)-2-benzylaminocyclohexyl(diphenyl)methanol showed the opposite (S)-selectivity (66.0% ee). The optically active 1,3-amino alcohols have been also shown to catalyze the asymmetric arylation of aryl aldehydes using boronic acids as the source of transferable aryl groups, with good yields and moderate to high enantioselectivities (up to >99% ee). The results demonstrated that the substituents to the vicinity of hydroxyl group have a crucial effect on chirality control. The substituent effect of 1,3-amino alcohols was confirmed for all the aromatic aldehydes studied. Both enantiomers of a product could be obtained by using the ligands with the same chirality. In addition, a good linear correlation was observed between the enantioselectivity and the electronic propertiy of the substituents on a substrate (The stronger electron-withdrawing substituents on the para-position exhibited higher enantiomeric excess, while the stronger electron-donation substituents on the para-position showed lower selectivity). |
|||||
注記 | ||||||
内容記述タイプ | Other | |||||
内容記述 | 指導教員: 埼玉大学大学院理工学研究科教授 廣瀬卓司 | |||||
資源タイプ | ||||||
内容記述タイプ | Other | |||||
内容記述 | text | |||||
フォーマット | ||||||
内容記述タイプ | Other | |||||
内容記述 | application/pdf | |||||
作成日 | ||||||
日付 | 2010-03-10 | |||||
日付タイプ | Created | |||||
アイテムID | ||||||
GD0000147 |