2023 Fiscal Year Final Research Report
Generation of Novel Allenylidene Complexes Based on Activation of Alkynylstannanes and their Application in Catalytic Reactions
| Project/Area Number |
21K05049
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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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| Review Section |
Basic Section 33020:Synthetic organic chemistry-related
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| Research Institution | Chitose Institute of Science and Technology |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
是永 敏伸 岩手大学, 理工学部, 教授 (70335579)
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| Project Period (FY) |
2021-04-01 – 2024-03-31
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| Keywords | 金 / アレニリデン金錯体 / シクロプロパン化反応 / 環拡大反応 / 1,5-エンイン / プロパルギル位置換反応 / 環化異性化反応 / タンデム反応 |
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| Outline of Final Research Achievements |
The present study aimed to investigate the generation and reactivities of allenylidene-gold(I) complexes. The reaction of propargylic esters having tributylstannyl group at alkyne terminus with styrene derivatives in the presence of a cationic gold(I) catalyst afforded vinylidene cyclopropane derivatives as a mixture of diastereomers. Interestingly, the cis-geometry of the alkenes is retained almost completely in the product. Mechanistic investigations and DFT calculation revealed that the gold(I)-acetylide species as a resonance form of gold(I)-coordinated allenylidene species involved. Furthermore, we found that the gold(I)-catalyzed reaction of stannylated propargyl acetates with indenes yielded 2-vinyl-substituted naphthalene derivatives, which would proceed through a tandem cyclopropanation/ring-expansion reaction.
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| Free Research Field |
有機合成化学
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| Academic Significance and Societal Importance of the Research Achievements |
金カルベンを経る触媒反応の開発において，一価のアレニリデン金中間体を触媒活性種として用いる炭素－炭素結合形成反応は未だに報告例がなく黎明期にある。本研究では，アレニリデン金中間体の新規発生法を見出しただけでなく，その真の反応活性種がアレニリデン金中間体の共鳴構造体である金アセチリド中間体であるという学術的に新規な知見を得ることもできた。さらに，ビニリデンシクロプロパン誘導体を反応中間体と捉えたタンデム触媒反応の開発も開発することができた。本手法は，多環式芳香族化合物の合成も実現できることから，機能性材料開発および医薬品開発に進展をもたらすことが期待される。
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