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

被引：39

作者：

Motoyoshiya, J ^{[1
]}

Kusaura, T ^{[1
]}

Kokin, K ^{[1
]}

Yokoya, S ^{[1
]}

Takaguchi, Y ^{[1
]}

Narita, S ^{[1
]}

Aoyama, H ^{[1
]}

机构：

[1] Shinshu Univ, Fac Text Sci & Technol, Dept Chem, Ueda, Nagano 3868567, Japan

来源：

TETRAHEDRON | 2001年 / 57卷 / 09期

关键词：

Horner-Wadsworth-Emmons reaction; phosphonoacetate; selectivity; substituent effect;

D O I：

10.1016/S0040-4020(01)00007-2

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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 P-31 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. (C) 2001 Elsevier Science Ltd. All rights reserved.

引用

页码：1715 / 1721

页数：7

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