Generation of nitroalkanes, hydroximoyl halides and nitrile oxides from the reactions of β-nitrostyrenes with Grignard or organolithium reagents

Ching-Fa Yao, Kuo Hsi Kao, Ju Tsung Liu, Cheng Ming Chu, Yeh Wang, Wen Chang Chen, Yu Mei Lin, Wen-Wei Lin, Ming Chung Yan, Jing Yuan Liu, Ming Ching Chuang, Jin Lien Shiue

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Abstract

The β-nitrostyrenes 1 or 2 react with Grignard or organolithium reagents in ether or THF solution to generate by 1,4-addition the intermediate nitronates A. When A is treated with dilute hydrochloric acid, high yields of the nitroalkanes 3 (and oximes 4) or 5 are obtained Hydroximoyl halides 6, 8 or nitrile oxides 7 can be isolated when the intermediate A is slowly added to the ice cold concentrated hydrohalic acid. The same products 6 and/or 7 are observed if the nitronates, generated from the substrate 1a, are added to 85% aqueous H2SO4 but only the hydrolyzed carboxylic acids 9 are generated when the β-nitrostyrenes 2 are reacted with Grignard reagents and worked up under the same condition. The nitrile oxides 7 can undergo 1,3-dipolar cycloaddition with alkenes or alkynes to generate 2-isoxazolines or isoxazoles. A one-pot synthesis of the [n,3,0] bicyclic (n = 3 or 4) compounds 23-27 by intramolecular nitrile oxide-olefin cycloadditions is reported.

Original languageEnglish
Pages (from-to)791-822
Number of pages32
JournalTetrahedron
Volume54
Issue number5-6
DOIs
Publication statusPublished - 1998 Jan 29

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Nitriles
Oxides
Cycloaddition
Cycloaddition Reaction
Alkenes
Isoxazoles
Oximes
Alkynes
Hydrochloric Acid
Ice
Carboxylic Acids
Ether
Acids
Substrates

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Generation of nitroalkanes, hydroximoyl halides and nitrile oxides from the reactions of β-nitrostyrenes with Grignard or organolithium reagents. / Yao, Ching-Fa; Kao, Kuo Hsi; Liu, Ju Tsung; Chu, Cheng Ming; Wang, Yeh; Chen, Wen Chang; Lin, Yu Mei; Lin, Wen-Wei; Yan, Ming Chung; Liu, Jing Yuan; Chuang, Ming Ching; Shiue, Jin Lien.

In: Tetrahedron, Vol. 54, No. 5-6, 29.01.1998, p. 791-822.

Research output: Contribution to journalArticle

Yao, Ching-Fa ; Kao, Kuo Hsi ; Liu, Ju Tsung ; Chu, Cheng Ming ; Wang, Yeh ; Chen, Wen Chang ; Lin, Yu Mei ; Lin, Wen-Wei ; Yan, Ming Chung ; Liu, Jing Yuan ; Chuang, Ming Ching ; Shiue, Jin Lien. / Generation of nitroalkanes, hydroximoyl halides and nitrile oxides from the reactions of β-nitrostyrenes with Grignard or organolithium reagents. In: Tetrahedron. 1998 ; Vol. 54, No. 5-6. pp. 791-822.
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AU - Chu, Cheng Ming

AU - Wang, Yeh

AU - Chen, Wen Chang

AU - Lin, Yu Mei

AU - Lin, Wen-Wei

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AU - Chuang, Ming Ching

AU - Shiue, Jin Lien

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