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

29 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

Fingerprint

Phosphonoacetic Acid
Aldehydes
Electrons
Crown Ethers
Organophosphonates
Chemical shift
Cations
Metals

Keywords

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

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

The Horner-Wadsworth-Emmons reaction of mixed phosphonoacetates and aromatic aldehydes : Geometrical selectivity and computational investigation. / Motoyoshiya, Jiro; Kusaura, Tatsuya; Kokin, Keisuke; Yokoya, Sei Ichi; Takaguchi, Yutaka; Narita, Susumu; Aoyama, Hiromu.

In: Tetrahedron, Vol. 57, No. 9, 25.02.2001, p. 1715-1721.

Research output: Contribution to journalArticle

Motoyoshiya, Jiro ; Kusaura, Tatsuya ; Kokin, Keisuke ; Yokoya, Sei Ichi ; Takaguchi, Yutaka ; Narita, Susumu ; Aoyama, Hiromu. / The Horner-Wadsworth-Emmons reaction of mixed phosphonoacetates and aromatic aldehydes : Geometrical selectivity and computational investigation. In: Tetrahedron. 2001 ; Vol. 57, No. 9. pp. 1715-1721.
@article{4ccba6a79a024eb9889c5d7442c1fd41,
title = "The Horner-Wadsworth-Emmons reaction of mixed phosphonoacetates and aromatic aldehydes: Geometrical selectivity and computational investigation",
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.",
keywords = "Horner-Wadsworth-Emmons reaction, Phosphonoacetate, Selectivity, Substituent effect",
author = "Jiro Motoyoshiya and Tatsuya Kusaura and Keisuke Kokin and Yokoya, {Sei Ichi} and Yutaka Takaguchi and Susumu Narita and Hiromu Aoyama",
year = "2001",
month = "2",
day = "25",
doi = "10.1016/S0040-4020(01)00007-2",
language = "English",
volume = "57",
pages = "1715--1721",
journal = "Tetrahedron",
issn = "0040-4020",
publisher = "Elsevier Limited",
number = "9",

}

TY - JOUR

T1 - The Horner-Wadsworth-Emmons reaction of mixed phosphonoacetates and aromatic aldehydes

T2 - Geometrical selectivity and computational investigation

AU - Motoyoshiya, Jiro

AU - Kusaura, Tatsuya

AU - Kokin, Keisuke

AU - Yokoya, Sei Ichi

AU - Takaguchi, Yutaka

AU - Narita, Susumu

AU - Aoyama, Hiromu

PY - 2001/2/25

Y1 - 2001/2/25

N2 - 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.

AB - 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.

KW - Horner-Wadsworth-Emmons reaction

KW - Phosphonoacetate

KW - Selectivity

KW - Substituent effect

UR - http://www.scopus.com/inward/record.url?scp=0035945995&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035945995&partnerID=8YFLogxK

U2 - 10.1016/S0040-4020(01)00007-2

DO - 10.1016/S0040-4020(01)00007-2

M3 - Article

AN - SCOPUS:0035945995

VL - 57

SP - 1715

EP - 1721

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 9

ER -