1992 Fiscal Year Final Research Report Summary
DIENE-DIENOPHILE METATHESIS : A NOVEL METHYLENE MIGRATION REACTION
| Project/Area Number |
02804040
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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 |
有機化学一般
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| Research Institution | Osaka Kyoiku University |
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Principal Investigator |
TOHDA Yasuo Osaka Kyoiku University, Department of Education, Professor, 教育学部, 教授 (10127342)
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| Co-Investigator(Kenkyū-buntansha) |
ARIGA Masahiro Osaka Kyoiku University, Department of Education, Professor, 教育学部, 教授 (90030395)
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| Project Period (FY) |
1990 – 1992
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| Keywords | Diene-Dienophile Metathesis / Six-membered Cyclic Nitronate / Nitroalkene / alpha,beta-Unsaturated Oxime / Reverse Diels-Alder Decomposition |
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| Research Abstract |
A new reaction, "Diene-Dienophile Metathesis" was investigated which was defined as follow : The reaction is constructed by three consecutive elementary reactions. The first is either Diels-Alder or reverse electron-demand Diels-Alder addition of "diene" and "dienophile". The second is 1,3-prototrophy of the adduct. The third is Diels-Alder decomposition of the isomerized adduct to a rearranged "diene" and "dienophile".
We found that nitroalkenes having an electron-withdrawing group such as p-nitrophenyl or sulfonyl groups were good "diene" to give alpha,beta-unsaturated oximes in which the beta-methylene carbon was migrated from the "dienophile". Vinyl ethers were found to be a good "dienophile", while vinyl sulfides derived from aldehydes could not act as "dienophile" because undesirable side reaction occurred.
A key intermediate is a six-membered cyclic nitronate and formation and the decomposition of the compound was investigated. 3,5-Dinitro-2-pyridines was found to react with ethyl vinyl ethers to give the nitronate.
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