Investigation on the behavior of anionic transition metal complexes and their application for the catalytic transformations
| Project/Area Number |
16H06039
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| Research Category |
Grant-in-Aid for Young Scientists (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | The University of Tokyo (2018)
Osaka University (2016-2017) |
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Principal Investigator |
Iwasaki Takanori 東京大学, 大学院工学系研究科(工学部), 准教授 (50550125)
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| Project Period (FY) |
2016-04-01 – 2019-03-31
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| Project Status |
Completed (Fiscal Year 2018)
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| Budget Amount *help |
¥25,740,000 (Direct Cost: ¥19,800,000、Indirect Cost: ¥5,940,000)
Fiscal Year 2018: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000)
Fiscal Year 2017: ¥7,800,000 (Direct Cost: ¥6,000,000、Indirect Cost: ¥1,800,000)
Fiscal Year 2016: ¥11,830,000 (Direct Cost: ¥9,100,000、Indirect Cost: ¥2,730,000)
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| Keywords | 遷移金属触媒 / アート型錯体 / 炭素ー炭素結合形成反応 / クロスカップリング反応 / 多成分連結反応 / クロスカップリング / 合成化学 / 有機金属化学 / ニッケル / コバルト / 鉄 / 銅 / 多成分反応 / C-F結合活性化 / アルキル化反応 / C-F結合 / パーフルオロアレーン |
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| Outline of Final Research Achievements |
We developed various catalytic systems which effectively promote cross-coupling reaction of alkyl halides with alkyl Grignard reagents to construct saturated hydrocarbon frameworks. As a functionalization of 1,3-butadiene, we developed internal carbon selective alkylation reaction by copper catalyst with alkyl fluorides. When Ni was used instead of Cu, dimerization and double functionalization by carbon nucleophiles and carbon electrophiles proceeded to give mulit component coupling products.
In these catalytic reactions, anionic transition metal complexes arising from transition metal complex with organometallic reagents were found to be the catalytic active species.
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| Academic Significance and Societal Importance of the Research Achievements |
遷移金属触媒において「遷移金属をアニオン性錯体にする」というコンセプトのもと、高難度分子変換反応を実現した。従来の遷移金属触媒の多くは中性およびカチオン性の遷移金属錯体が用いられてきたが、これをアニオン性とし、対カチオンとの協同触媒効果を利活用することにより、炭素ーフッ素結合といった極めて結合切断が困難な化学結合すら有機合成化学に利用できることを明らかにした。さらに、この化学的に強固な結合を合成化学に利用することにより、従来手法では困難な合成戦略を提案することが可能である。
これらの成果は、新たな触媒設計指針として有機合成化学・触媒化学分野に貢献するものである。
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Report
(4 results)
Research Products
(70 results)
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[Journal Article] Nickel-Catalyzed Direct Alkylation of Thiophenes via Double C(sp3)-H/C(sp2)-H Bond Cleavage: The Importance of KH2PO42017
Author(s)
Xie Wang, Peipei Xie, Renhua Qiu, Longzhi Zhu, Ting Liu, You Li, Takanori Iwasaki, Chak-Tong Au, Xinhua Xu, Yuanzhi Xia, Shuang-Feng Yin, and Nobuaki Kambe
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Journal Title
Chem. Commun.
Volume: 53
Issue: 59
Pages: 8316-8319
DOI
Related Report
Peer Reviewed / Int'l Joint Research
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[Journal Article] Intramolecular, Site-Selective, Iodine-Mediated, Amination of Unactivated (sp3)C-H Bonds for the Synthesis of Indoline Derivatives2017
Author(s)
Jinguo Long, Xin Cao, Longzhi Zhu, Renhua Qiu, Chak-Tang Au, Shuang-Feng Yin, Takanori Iwasaki, and Nobuaki Kambe
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Journal Title
Org. Lett.
Volume: 19
Issue: 11
Pages: 2793-2796
DOI
Related Report
Peer Reviewed / Int'l Joint Research
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