Stereochemical behavior of intermediary compounds in the amine-catalyzed Knoevenagel reaction.

• Tanikaga Rikuhei

  Department of Chemistry, Faculty of Science, Kyoto University

• Konya Naoto

  Department of Chemistry, Faculty of Science, Kyoto University

• Hamamura Kazumasa

  Department of Chemistry, Faculty of Science, Kyoto University

• Kaji Aritsune

  Department of Chemistry, Faculty of Science, Kyoto University

Abstract

Treatment of the active methylene compounds and aldehydes with a catalytic amount of a secondary amine produces thermodynamically stable alkenes, and the intermediary amino compounds are isolated. The reaction involves many reversible steps, and the stereochemistry of products is determined in the elimination step from the intermediary compounds via stable planar carbanions, in which the small difference in the steric requirements of two electron-withdrawing groups is effective. Steric and electronic effects in the intermediates sometimes bring about the carbon–carbon bond fission with recovery of active methylene compounds, and these effects prevent the Knoevenagel reaction from occurring.

Journal

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 61 (9), 3211-3216, 1988

  The Chemical Society of Japan

Keywords

• General Chemistry

Details

• CRID: 1390001204121151872
• NII Article ID: 130001980879
• DOI: 10.1246/bcsj.61.3211
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/61/9/3211/55726786/bcsj.61.3211.pdf
• Text Lang: en
• Data Source:
  • JaLC
  • Crossref
  • CiNii Articles
• Abstract License Flag: Disallowed