2019 Fiscal Year Annual Research Report
Triphosphine ligand-enabled iron catalysis
Publicly Offered Research
| Project Area | Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions |
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| Project/Area Number |
18H04238
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| Research Institution | Institute of Physical and Chemical Research |
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Principal Investigator |
イリエシュ ラウレアン 国立研究開発法人理化学研究所, 環境資源科学研究センター, チームリーダー (40569951)
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| Project Period (FY) |
2018-04-01 – 2020-03-31
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| Keywords | organic synthesis / catalysis |
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| Outline of Annual Research Achievements |
This project aims at the creation of a ligand that can control the reactivity of organoiron species and achieve an efficient and versatile iron catalyst for organic synthesis, surpassing precious metal catalysis. We discovered that an iron/diphosphine catalyst, in the presence of a diorganozinc base and a mild dichloroalkane oxidant enables the stoichiometric cross-coupling of aromatic amides with heteroarenes. The cross-coupling of two different C-H substrates is especially difficult because of competing homocoupling, and typically a large excess of one of the coupling partners must be used; however, the iron catalyst enabled the cross-coupling with perfect selectivity, and homocoupling of the starting materials was not observed at all. The reaction could also be applied to efficient multifold C-H cross-coupling. For example, three C-H bonds in a tris-thiophene molecule could be coupled with three amide molecules’ C-H bonds to create three new C-C bonds in almost quantitative yield. Mechanistic studies suggested that directed C-H activation of the amide takes place first, then the resulting iron intermediate activates the C-H bond of the heteroarene in a reversible fashion. Preliminary results showed that electron-deficient arenes such as chlorobenzene can also be used as the reaction partner.
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| Research Progress Status |
令和元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 |
令和元年度が最終年度であるため、記入しない。
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