Sodium methoxide catalyzed isomerization of dimethyl 1-oxo-cis-3a,7a-dihydroindene-3a,7a-dicarboxylates to dimethyl 3-oxo-1,7-indandicarboxylates.

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概要

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• Treatment of dimethyl 1-oxo-<I>cis</I>-3a,7a-dihydroindene-3a,7a-dicarboxylates (<B>A</B>) with sodium methoxide in methanol gave particular dimethyl 3-oxo-1,7-indandicarboxylates (<B>F</B>). A multistep mechanism for the isomerization was proposed on the basis of the positional correlations between the dihydroindenones <B>A</B> and the corresponding isomers <B>F</B>. The isomerization seems to be initiated by the addition of a methoxide to the 1 position of the dihydroindenones <B>A</B> affording the cyclohexadienide anions (<B>B</B>), which cyclize to give dimethyl 1-oxo-<I>cis</I>-3a,7a-dihydroindene-3a,4-dicarboxylates (<B>C</B>). The dihydroindenones <B>C</B> become enolates (<B>D</B>), whose methoxycarbonyl group at the 3a position (E<SUB>9</SUB>) shifts to the 1 position of the enolates of <B>F</B>, (<B>E</B>), with the aid of aromatization. The same treatment of methyl 3-oxo-<I>cis</I>-3a,7a-dihydroindene-3a-carboxylates gave key information on the process for the isomerization of <B>A</B>.

• 公益社団法人 日本化学会の論文

著者

• Uyehara Tadao

  Department Of Applied Chemistry Faculty Of Engineering Utsunomiya University

• Kitahara Yoshio

  Department of Chemistry, Faculty of Science, Tohoku University

• Kitahara Yoshio

  Department Of Chemistry Faculty Of Science Tohoku University

• Miyakoshi Shoichi

  Department of Chemistry, Faculty of Science, Tohoku University

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