Chemistry of dienyl anions. II. Crystalline bis(dienyl)magnesium. Selective dienylation and structure in solution and in the solid state.

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概要

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• Seven different crystalline bis(dienyl)magnesium·TMEDA complexes of open chain or cyclic structure were prepared by metal exchange reaction of corresponding potassium dienides. They are fluxional in solution due to the rapid 1,3-rearrangement. Terminally σ-bonded <I>trans</I> or (<I>E</I>) structure exists primarily in the open chain complexes while centrally σ-bonded <I>cis</I> structure in cyclic dienylmagnesium·TMEDA complexes. The former gave 1,3-dienes exclusively but the latter gave 1,4-dienes upon hydrolysis. Molecular structure of bis(2,4-dimethyl-2,4-pentadienyl)magnesium determined by X-ray crystallography showed that it has terminally σ-bonded structure. Addition of dienylmagnesium compounds to acetone followed by hydrolysis gave 1,4-diene derivatives regioselectively but that to diisopropyl ketone gave 1,3-diene derivatives selectively. Unsaturated alcohols with an elongated carbon chain were synthesized by thermal cracking of cyclic ether complexes. 1,3,7-Trienes can be obtained selectively by reaction of appropriate allyl halides in the presence of CuCl catalyst and regioselective dienylation occurred by using TiCl<SUB>2</SUB>(η<SUP>5</SUP>-C<SUB>5</SUB>H<SUB>5</SUB>)<SUB>2</SUB> as catalyst.

• 公益社団法人 日本化学会の論文

著者

• Kai Yasushi

  Department Of Applied Chemistry Faculty Of Engineering Osaka University

• Yasuda Hajime

  Department Of Applied Chemistry Faculty Of Engineering Hiroshima University

• Kasai Nobutami

  Department Of Applied Biological Science Tokyo University Of Science

• Yasuoka Noritake

  Department Of Life Science Faculty Of Science Himeji Institute Of Technology

• Nakamura Akira

  Department Oc Macromolecular Science Faculty Of Science Osaka University

• Yamauchi Michihide

  Department of Macromolecular Science, Faculty of Science, Osaka University

• Sei Tsuyoshi

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

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