1997 Fiscal Year Final Research Report Summary
Development of Transition-Metal Catalyzed Methods for the Construction of Carbon Skeletotnes under the Neutral Conditions
| Project/Area Number |
08455424
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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 | Nagoya University |
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Principal Investigator |
MATSUDA Isamu Nagoya University, Graduate School of Engineering Associate Professor, 工学研究科, 助教授 (80023266)
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| Project Period (FY) |
1996 – 1997
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| Keywords | Silylformylation / Rhodium-catalyst / Hydrosilane / Cylocarbonylation / Carbon monoxide / 1,6-Heptadiyne |
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| Research Abstract |
The present research aims to develop new reactions catalyzed by transition-metal complexes for the construction of carbon-carbon bond. Thus, our interest is focused to the following two subjects ; I) direct incorporation of carbon monoxide as the carbonyl source and ii) establishment of a new method for the construction of carbocycles under neutral conditions. Firstly, silylformylation of an acetylenic triple bond was subjected in detail because it will give a good barometer on the catalytic activation of carbon-carbon triple bonds. As a result, the following two aspects were revealed ; the presence of rhodium catalyst is crucial in order to attain the reaction and the start of the catalytic cycle is oxidative addition of a hydrosilane to a rhodium metal. A complete regioselection for the silylformylation of internal acetylenes was also realized by the intramolecular version. When alkynylamines and alkynols were subjected to silylformylation, the addition of catalytic amount of DBU drastically changed reaction path to give lactams (4-8 membered rings) and lactones (4-7 membered rings).
Secondly, a new type of annulation method was found under the conditions similar to silyformylation. 1,6-Heptadiyne derivatives gave the corresponding bicyclo [3.3.0] octenones in the rhodium-catalyzed reaction with a hydrosilane and CO.The major product obtained from the reaction of 4,4-dimethy1-3-trimethylsiloxyhepta-1,6-diyne was able to be lead to the key intermediate for the synthesis of coriolin by the additional steps, hydrogenation, methylation, and methallylation. 1,2-Bismethylenecyclopentane derivatives were also constructed by the Rh-catalyzed reaction of 1,6-heptadiyne derivatives with hydrosilane in the absence of CO.
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