| Project/Area Number |
18H01986
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Review Section |
Basic Section 33020:Synthetic organic chemistry-related
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| Research Institution | National Institute of Advanced Industrial Science and Technology |
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Principal Investigator |
Nakajima Yumiko 国立研究開発法人産業技術総合研究所, 材料・化学領域, 研究チーム長 (80462711)
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| Project Period (FY) |
2018-04-01 – 2021-03-31
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| Project Status |
Completed (Fiscal Year 2020)
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| Budget Amount *help |
¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000)
Fiscal Year 2020: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2019: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000)
Fiscal Year 2018: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000)
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| Keywords | クロロシラン / 遷移金属錯体触媒 / 結合切断 / シリコーン / 低原子価金属錯体 / クロスカップリング反応 / 有機ケイ素化合物 / ニッケル触媒 / 鉄錯体 / 不活性結合切断 / 四座PNNP配位子 / 錯体触媒 |
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| Outline of Final Research Achievements |
This research aims at development of catalytic systems to produce organosilicon compounds from chlorosilanes as versatile and cheap silicon feedstocks. To this end, we also performed detailed mechanistic study on the key reaction step, oxidative addition of a strong Si-Cl bond, which has not been clarified academically. Through this study, silyl-Heck reaction was developed to achieve selective monoalkenylization of polychlorosilane using electron-rich nickel catalysts. A selective alkylation reaction of chlorosilane using highly versatile alkylaluminum as a coupling partner was also achieved by combination of nickel or palladium precursors with a phosphorus-based ligand. By using these reactions, it has become possible to efficiently synthesize various organochlorosilanes, which has been difficult to synthesize by conventional methods.
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| Academic Significance and Societal Importance of the Research Achievements |
有機ケイ素化合物は有機合成における鍵中間体やシリコーン原料として重要な化合物である。有機ケイ素化合物の一般的な合成手法として、工業的直接法により安価かつ大量に供給可能なクロロシランと有機金属試薬との量論反応が知られるが、本手法は ①反応性の高い有機金属試薬を利用するため、導入する置換基の種類が限定的、②量論量の有機金属試薬を用いるため、多くの副生成物を生じる、といった問題点を抱える。したがって、クロロシランを原料として、様々な有機ケイ素化合物の合成を可能とする“触媒反応”の開発は、極めて重要な課題である。
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