1990 Fiscal Year Final Research Report Summary
Development of New Reactive Intermediates on the Basis of the Reactions of Functionalized Highly Strained Molecules
| Project/Area Number |
63470013
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
NAKAMURA Eiichi Tokyo Institute of Technology ; Faculty of Science ; Associate Professor, 理学部, 助教授 (00134809)
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| Project Period (FY) |
1988 – 1990
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| Keywords | Cycloaddition / Tetrahydrofuran / Dicarbonyl compounds / Cyclopropene / Asymmetric synthesis / Five-membered rings |
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| Research Abstract |
Aim of the Research : This program is directed toward the development of new reactive intermediates and new reactions by taking advantage of the internal chemical energy stored in strained molecules.
Results : The following three reactions have been developed. (1) New thermal [3+2] cycloaddition. The reaction of 2, 2-dialkoxy-1-methylenecyclopropane with electron-deficient olefins under mild thermal conditions gives cyclopentanes in high yield. A similar reaction with carbonyl compounds affords substituted tetrahydrofurans. The mechanism and the nature of the reactive intermediate have been elucidated by kinetic and theoretical studies. (2) Carbometalation reaction. Addition of organometallics to cyclopropenone acetals provided a new entry to the chemistry of cyclopropyl metal compounds, which was further applied to the asymmetric synthesis of optically active compounds. (3) Synthesis of dicarbonyl compounds. Palladium-catalyzed reaction of cyclopropanone acetals with aryl triflates in the presence of carbon monoxide provided a new entry to the synthesis of 1, 4-dicarbonyl compounds.
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