2013 Fiscal Year Final Research Report
Efficient and Selective Formation of Phenylacetic Acids from Diketene
| Project/Area Number |
24655087
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Nagasaki University |
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Principal Investigator |
KIMURA Masanari 長崎大学, 工学(系)研究科(研究院), 教授 (10274622)
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| Project Period (FY) |
2012-04-01 – 2014-03-31
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| Keywords | ニッケル / 有機亜鉛 / 有機アルミニウム / アルキン / ジケテン |
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| Research Abstract |
In the presence of Ni catalyst, three components of diketene, alkyne, and Me2Zn combine smoothly to provide 3-methylene-4-hexenoic acids in excellent yields. Furthermore, under similar catalytic conditions, Et2Al(OEt) promotes [2+2+2] cycloaddition reactions with diketene and 2 equivalents of alkyne to give rise to the substituted phenylacetic acids. More interestingly, in the presence of Et2Al(OEt) and phosphine ligand, symmetrical phenyl acetic acids are constructed via the formal [2+2+1+1] cycloaddition reactions with diketene and 2 equivalents of alkyne accompanying the cleavage reaction of methylene C=C double bond of diketene.
This is the first example of the selective formation of unsaturated carboxylic acids and phenylacetic acids from diketene involving oxanickelacycles. The reaction presented here might be a powerful tool in the expedient synthesis of the physiologically active molecules, such as isoprenoid acids and non-steroidal anti-inflammatory drugs (NSAIDs).
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