2017 Fiscal Year Annual Research Report
Design of Iron Catalyst for Activation of Simple Arenes and Heteroarenes
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 |
16H01005
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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, 大学院理学系研究科(理学部), 准教授 (40569951)
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| Project Period (FY) |
2016-04-01 – 2018-03-31
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| Keywords | 有機合成 |
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| Outline of Annual Research Achievements |
This research project focused on the development of iron-catalyzed functionalization of simple arenes and heteroarenes, enabled by the design of new ligands.
The starting point of the project was the discovery that a triphosphine ligand uniquely enables iron-catalyzed methylation of weakly coordinating substrates such as carboxylic acids, esters, amides, and simple or functionalized ketones (J. Am. Chem. Soc. 2016, 138, 10132). However, this reaction was limited to methylation, using trimethylaluminum both as a methylating reagent, and as a base to assist cleavage of the C-H bond. In order to solve this problem, we engineered the aluminum reagent, and we have succeeded in the cyclative reaction of simple carbonyl compounds with electrophiles such as internal alkynes, to produce indenol derivatives (manuscript under preparation). Preliminary results also showed that by tuning the reaction conditions, reaction of carbonyl compounds with alkyl halides and with bis(pinacolato)diboron also proceeds, albeit in low yield (20-30%).
Another approach toward the activation of simple substrates is the development of iron-catalyzed reaction of N-(8-quinolyl)carboxamides with heteroarenes and electron-deficient arenes through double C-H bond activation (manuscript under preparation). Mechanistic investigations revealed that after directed C-H activation, the resulting ferracycle reversibly cleaves the C-H of the simple (hetero)arene.
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| Research Progress Status |
29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 |
29年度が最終年度であるため、記入しない。
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Research Products
(12 results)
