Synthesis of α β,-unsaturated amide via phosphonium ylide

Article abstract of DOI:10.1080/00397910802590902

A series of ,-unsaturated amides were prepared by the Wittig reaction of N,N-diethylamidemethylenetriphenylphosphorane ylide with aldehydes with moderate to good yields. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910802590902

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Synthesis of α,β-Unsaturated
Amide via Phosphonium Ylide
Shilei Jiang a , Kefeng Yang b & Xiaochun Yu a
a College of Chemistry and Materials Engineering ,
Wenzhou University , Zhejiang, China
b Huayi Pharmaceutical Co., Ltd. , Yiwu, Zhejiang,
China
Published online: 15 Apr 2009.
To cite this article: Shilei Jiang , Kefeng Yang & Xiaochun Yu (2009) Synthesis of
α,β-Unsaturated Amide via Phosphonium Ylide, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 39:10,
1759-1767, DOI: 10.1080/00397910802590902
To link to this article: http://dx.doi.org/10.1080/00397910802590902
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Synthetic Communications1, 39: 1759–1767, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802590902
Synthesis of a,b-Unsaturated Amide via
Phosphonium Ylide
Shilei Jiang,1 Kefeng Yang,2 and Xiaochun Yu1
1College of Chemistry and Materials Engineering, Wenzhou University,
Zhejiang, China
2Huayi Pharmaceutical Co., Ltd., Yiwu, Zhejiang, China
Abstract: A series of a,b-unsaturated amides were prepared by the Wittig
reaction of N,N-diethylamidemethylenetriphenylphosphorane ylide with alde-
hydes with moderate to good yields.
Keywords: N,N-Diethylamidemethylenetriphenylphosphorane
unsaturated amide, Wittig reaction
ylide,
a,b-
INTRODUCTION
The formation of a carbon–carbon double bond is one of the useful and
fundamental reactions in synthetic organic chemistry, particularly in
the synthesis of complex natural products with biological activity. a,b-
Unsaturated amides have been used as building blocks in organic
synthesis[1–3] to prepare natural products.[4] Moreover, a,b-unsaturated
amides show both biological[5–12] and insecticide activities.[13–16] Several
methods have appeared for their synthesis, involving the conversion of
a,b-unsaturated carboxylic acid into amide,[17,18] Knoevenagel conden-
sation,[19] rearrangement of 4-isoxazdine,[20] Co2Rh2-catalyzed amino-
carbonylation of alkynes,[21] Pt-catalyzed aminocarbonylation of
iodoalkenes or iodobenzene,[22–27] elimination of a,b-epoxyamides,[28]
Received July 2, 2008.
Address correspondence to Xiaochun Yu, College of Chemistry and Materials
Engineering, Wenzhou University, Zhejiang 325027, China. E-mail: xiaochunyu@
wzu.edu.cn
1759

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1760
S. Jiang, K. Yang, and X. Yu
and zinc-promoted reaction of bromoacetamide.[29] For most reported
methods of preparing a,b-unsaturated amides, there are the carbon–
carbon double bonds in the starting materials, or through elimination
or rearrangement the formation of a carbon–carbon double bond was
provided.
The Wittig reaction is one of the most versatile synthetic methods for
preparation of olefins.[30–35] It had been reported that a,b-unsaturated
amides were prepared through Wittig reaction via tellurium ylide or
arsonium ylide.[36,37] To the best of our knowledge, the synthesis of
a,b-unsaturated amide through reaction of phosphium ylide with alde-
hyde has been unexplored. As we all know, it was very difficult to prepare
dibutyltellurium or triphenyl arsonine, which were the starting materials
for preparation of tellurium ylide or arsonium ylide, and they are either
very unstable or very toxic. Herein, we report the synthesis of a,b-
unsaturated amide by the reaction of N,N-diethylamidemethylenetriphe-
nylphosphorane ylide with aldehyde.
RESULTS AND DISCUSSION
The synthesis of N,N-diethylamidemethylenetriphenylphosphorane ylide
2 has been reported,[38] which used methylentriphenylphosphorane and
carbamoylchloriden as the starting materials. We chose the traditional
method to prepare the ylide 2, which used triphenylphosphine and 2-
chloro-N,N-diethylacetamide as the starting materials and sodium hydro-
xide as the base (Scheme 1).
The reactions of the ylide 2 with aromatic aldehydes and alphatic
aldehydes ran smoothly and gave both moderate to good yields and iso-
mer ratios (Table 1).
In our experiment, the aromatic aldehyde with the electron-
withdrawing group reacted with the ylide easily and gave the higher yield
partly because the withdrawing group increased the activity of the C¼O
Scheme 1. Synthesis of a,b-unsaturated amide.