| Project/Area Number |
10450346
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Waseda University |
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Principal Investigator |
YAMAMOTO Akio Waseda University, Graduate School of Science and Engineering, Professor, 理工学研究科, 教授 (30016711)
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| Project Period (FY) |
1998 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥6,100,000 (Direct Cost: ¥6,100,000)
Fiscal Year 1999: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 1998: ¥3,300,000 (Direct Cost: ¥3,300,000)
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| Keywords | carboxylic acid / anhydride / aldehyde / hydrogenation / reduction / palladium / ester / carbon-oxygen bond activation / 炭素―酸素結合活性化 / パラジウム錯体 / 酸化的付加 / アシルパラジウム錯体 |
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| Research Abstract |
We have studied the carbon-oxygen bond activation of organic compounds by palladium complexes and its application to novel catalytic processes.
Major findings : (A) improvement of the reaction conditions of the diect hydrogenation of carboxylic acids to aldehydes by palladium complexes in the presence of pivalic anhydride was investigated. The hydrogenation reaction proceeded faster in polar solvents such as acetone and DMF. The nature of palladium-tertiary phosphine catalyst also affected the hydrogenation, the highest yield of aldehyde was obtained with use of palladium acetate and five equivalents of tri (p-tolyl) phosphine catalyst. The heterogeneous catalysts such as palladium on charcoal also catalyzed this hydrogenation reaction.
(B) carbon-oxygen bond of ketene dimer was cleaved by a zerovalent palladium-styrene complex having two tertiary phosphines to give corresponding palladalactone complex. The structure of the palladalactone complex was fully determined by X-ray crystallography and NMR spectroscopy. Study of the chemical reactivity of the palladalactone complex was also investigated.
(C) study on the oxidative carbonylation of amines catalyzed by palladium complexes was investigated. Oxamide was obtained in a good yield by using 1,4-dichloro-2-butene as an oxidizing agent.
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