Hydroalkylation of Simple Alkenes by sp3 C-H Bond
| Project/Area Number |
17K05867
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Aoyama Gakuin University |
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Principal Investigator |
Takeuchi Ryo 青山学院大学, 理工学部, 教授 (00216871)
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| Project Period (FY) |
2017-04-01 – 2020-03-31
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| Project Status |
Completed (Fiscal Year 2019)
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| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2019: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
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| Keywords | ヒドロアルキル化 / 単純アルケン / 1,3-ジケトン / β-ケトエステル / カチオン性イリジウム触媒 / 炭素-炭素結合生成 / 活性メチレン化合物 / イリジウム / 炭素‐水素結合活性化 / 炭素-水素結合活性化 / ヒドロアルキル化反応 |
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| Outline of Final Research Achievements |
Hydroalkylation of alkenes is a useful reaction to construct a carbon-carbon bond under neutral reaction conditions in a highly atom-economical manner. Intermolecular hydroalkylation of aliphatic terminal alkenes with 1,3-diketones under neutral conditions has been achieved using a cationic iridium catalyst. An active C-H bond of 1,3-diketones added to aliphatic terminal alkenes to give branched α-substituted 1,3-diketones in high yields. The products were easily converted to heterocycles. Similarly, hydroalkylation of aliphatic alkenes with β-ketoesters proceeded with the use of a cationic iridium complex and bidentate phosphine ligand to give selectively branched α-substituted β-ketoesters in high yields. One-pot sequential hydroalkylation/Krapcho dealkoxycarbonylation of alkenes and beta-ketoesters gave β-substituted ketones. These reactions provide a new method for extending a carbon chain from an aliphatic terminal alkene.
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| Academic Significance and Societal Importance of the Research Achievements |
大規模に製造され入手容易な原料である単純アルケンを用いる炭素-炭素結合生成反応の開発が待ち望まれている。例えば、Michael反応では、アルケンに電子吸引基が置換している必要があり、単純アルケンには適用できない。本研究は、単純アルケンから中性条件において原子効率的な炭素鎖伸長を実現した。これらの反応は、汎用化学原料の高付加価値化分子変換反応として極めて大きな意味をもつ。また、カチオン性イリジウム触媒の炭素-炭素結合生成反応に対する潜在的可能性を明らかにし、学術上の新たな課題を明確にした事は意義深い。
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Report
(4 results)
Research Products
(16 results)
