Dioxopyrrolines.XLII. : Mechanism of 7-Epimerization Reaction of 7-Substituted 5-Ethoxycarbonyl-1-phenyl-2-azabicyclo[3.2.0]heptane-3,4-diones

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概要

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• 7-Mono- and 7,7-disubstituted 5-ethoxycarbonyl-1-phenyl-2-azabicyclo[3.2.0]heptane-3,4-diones undergo epimerization at C-7 when treated when treated with base. Experiments using the stereospecifically deuterium labeled compound 6 showed that the inversion of stereochemistries at C-6 and C-7 took place simutaneously in this reaction, thus proving that the reaction proceeded through C_1-C_5 bond fission and recyclization. The suggested intermediate 10 with a highly strained seven membered ring would give either the C_7 epimerized product by a fast recombination or irreversibly give the dihydroazatropolones 9 by a trans- to cis- isomerization of the C=N double bond. Kinetic treatments showed that the latter reaction is slower than the former equilibrium reaction.The analogous 7-epimerization reaction observed in the hydride reduction of the 4-oxo group and in the photolysis of the imidate 24 was proved to proceed with a similar mechanism.

• 公益社団法人日本薬学会の論文
• 1989-03-25

著者

• 津田 喜典

  Faculty of Pharmaceutical Sciences, Kanazawa University

• 津田 喜典

  Faculty Of Pharmaceutical Sciences Kanazawa University

• 佐野 武弘

  Showa College of Pharmaceutical Sciences.

• 堀口 よし江

  昭和薬大

• 津田 喜典

  金沢大薬

• 堀口 よし江

  Showa College of Pharmaceutical Sciences

• 田中 和彦

  Showa College Of Pharmaceutical Sciences

• 阿部 健一

  鐘紡

• 阿部 健一

  Showa College of Pharmaceutical Sciences

• 佐野 武弘

  Showa Pharmaceutical Univ. Tokyo Jpn

• 佐野 武弘

  Showa College Of Pharmaceutical Sciences

• 堀口 よし江

  Showa College Of Pharmaceutical Sciences University Of Kanazawa

• 阿部 健一

  Traditional Chinese Medicine Research Laboratories., Kanebo, Ltd.,

• 阿部 健一

  Traditional Chinese Medicine Research Laboratories. Kanebo Ltd.

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