| Project/Area Number |
60550588
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Kyoto University |
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Principal Investigator |
TSUDA Tetsuo Kyoto University, Faculty of Eng, Assoc. Prof, 工学部, 助教授 (10025992)
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| Project Period (FY) |
1985 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1986: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1985: ¥1,300,000 (Direct Cost: ¥1,300,000)
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| Keywords | Transition metal carboxylate complex / Decarboxylative carbon-carbon bond formation / 二酸化炭素固定反応 / ギ酸による脱炭酸的還元 |
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| Research Abstract |
Development of novel and useful synthetic methods using a specific reactivity of transition metal carboxylate complexes was investigated.
(1) <Pd(PPh_3)_4> catalyzed a decarboxylative allylic alkylation of allylic acetates with <beta> -keto acids at room temperature to produce <alpha> -allylic ketones in good yields.
(2) <Pd(PPh_3)_4> catalyzed a decarboxylative allylic alkylation of 1,3-diene monoepoxides with <beta> -keto acids at room temperature to produce keto allylic alcohols in moderate to good yields.
These two reactions with high regio- and stereoselectivity provide a useful method of the carbon-carbon bond formation involving carbonyl and/or hydroxyl functional groups and are characterized by the facile decarboxylation of palladium( <II> ) <beta> -ketocarboxylate intermediates. It is highly interesting to note that these reactions proceed with a nucleophilic attack of enolate anions toward <pi> -allylpalladium( <II> ) complexes in the presence of free carboxylic acids.
(3) <Pd(PPh_3)_4> catalyzed a decarboxylative reduction of 1,3-diene monoepoxides with formic acid at room temperature to produce homoallylic alcohols in moderate yields.
(4) An equimolar amount of Ni(O)-tertiary phosphine complexes effected a cycloaddition of diynes and carbon dioxide at 130 ゜C to produce bicyclic <alpha> -pyrones. The diynes showed a different reactivity from monoynes. The bicyclic <alpha> -pyrone formation may be assumed to involve cyclic organonickel carboxylate intermediates, the reductive elimination of which produces the bicyclic <alpha> -pyrones. Development of a nickel-catalyzed bicyclic <alpha> -pyrone formation may be expected on the basis of the present stoichiometric reaction.
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