The Horner-Wadsworth-Emmons reaction of mixed phosphonoacetates and aromatic aldehydes: Geometrical selectivity and computational investigation

Jiro Motoyoshiya, Tatsuya Kusaura, Keisuke Kokin, Sei Ichi Yokoya, Yutaka Takaguchi, Susumu Narita, Hiromu Aoyama

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The substituent effect on the geometrical selectivity in the Horner-Wadsworth-Emmons (HWE) reaction was studied employing several mixed phosphonoacetates. Their reactions with aromatic aldehydes showed a gradual change in Z-selectivity according to the electron-withdrawing ability of the phosphonate substituents, and there was a good correlation between the observed selectivities and 31P chemical shifts of the phosphonoacetates. Some variables such as the metal cation and crown ether also affected the selectivity. A computational study using ab initio and semi-empirical calculations suggests that the electron-withdrawing substituents stabilize the intermediates as well as the transition states, which reduces the reversibility to increase Z-products. This is in agreement with the experimentally observed selectivity.

Original languageEnglish
Pages (from-to)1715-1721
Number of pages7
JournalTetrahedron
Volume57
Issue number9
DOIs
Publication statusPublished - Feb 25 2001
Externally publishedYes

Keywords

  • Horner-Wadsworth-Emmons reaction
  • Phosphonoacetate
  • Selectivity
  • Substituent effect

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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