Iron-Catalyzed C(sp3)-H Bond Functionalization
Publicly Offered Research
| Project Area | Molecule Activation Directed toward Straightforward Synthesis |
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| Project/Area Number |
25105711
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| Research Category |
Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | The University of Tokyo |
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Principal Investigator |
イリエシュ ラウレアン 東京大学, 理学(系)研究科(研究院), 准教授 (40569951)
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| Project Period (FY) |
2013-04-01 – 2015-03-31
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| Project Status |
Completed (Fiscal Year 2014)
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| Budget Amount *help |
¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000)
Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2013: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
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| Keywords | iron catalysis / C-H activation / iron |
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| Outline of Annual Research Achievements |
Iron-catalyzed C-H bond activation is of much interest because economic and environmental merits of iron, but the reactivity of catalytic organoiron species is difficult to control, hampering the development of efficient and selective reactions. We have developed the reaction of pivaloylamides with organozinc reagents in FY2014, but poor control of the reactivity of organoiron species resulted in very narrow reaction scope and little practicality.
In order to solve these problems, in FY 2015 we have developed a new catalytic system based on organoiron(III) species. Thus, we discovered that the use of a bidentate directing group, a diphosphine ligand and a mild organometallic reagent enables an organoiron(III)-catalyzed C-H bond activation reaction that shows broad scope and versatility. The iron(III) catalytic system was used for the follwing two reactions.
1) Oxidative reaction of (hetero)arene and alkeneamides with aryl-, alkenyl-, and alkyl boronates. This reaction is the first example of stereospecific diene and triene synthesis via C-H bond activation, and demonstrates the versatility of the organoiron(III) catalyst.
2) Iron-catalyzed alkylation of (hetero)arene and alkeneamides with primary and secondary alkyl tosylates and halides. This reaction is the first example of efficient C-H alkylation with alcohol derivatives.
With the new iron(III) catalytic system in hand, we are now pursuing the development of efficient C(sp3) activation reactions, and preliminary results show that a pivaloylamide can be efficiently arylated and alkenylated with organoborate reagents.
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| Research Progress Status |
26年度が最終年度であるため、記入しない。
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| Strategy for Future Research Activity |
26年度が最終年度であるため、記入しない。
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Report
(2 results)
Research Products
(47 results)
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[Presentation] ジ亜鉛中間体を経た選択的な置換インドール合成2015
Author(s)
Mayuko Isomura, Shinichi Yamauchi, Laurean Ilies, Masaharu Nakamura, Eiichi Nakamura
Organizer
日本化学会第95春季年会
Place of Presentation
日本大学（千葉）
Year and Date
2015-03-26 – 2015-03-29
Related Report
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[Presentation] Iron-Catalyzed C-H Activation2015
Author(s)
Laurean Ilies, Eiichi Nakamura
Organizer
The 13th Ibn Sina International Conference on Pure and Applied Heterocyclic Chemistry,
Place of Presentation
Hurghada (Egypt)
Year and Date
2015-02-14 – 2015-02-17
Related Report
Invited
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[Book] Organic Reactions2014
Author(s)
Eiichi Nakamura, Takuji Hatakeyama, Shingo Ito, Kentaro Ishizuka, Laurean Ilies, Masaharu Nakamura
Total Pages
206
Publisher
John Wiley&Sons
Related Report
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