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

研究成果査読

37 被引用数 (Scopus)

抄録

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.

本文言語English
ページ(範囲)1715-1721
ページ数7
ジャーナルTetrahedron
57
9
DOI
出版ステータスPublished - 2月 25 2001
外部発表はい

ASJC Scopus subject areas

  • 生化学
  • 創薬
  • 有機化学

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