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

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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  • Cite this

    Yao, C. F., Kao, K. H., Liu, J. T., Chu, C. M., Wang, Y., Chen, W. C., Lin, Y. M., Lin, W. W., Yan, M. C., Liu, J. Y., Chuang, M. C., & Shiue, J. L. (1998). Generation of nitroalkanes, hydroximoyl halides and nitrile oxides from the reactions of β-nitrostyrenes with Grignard or organolithium reagents. Tetrahedron, 54(5-6), 791-822. https://doi.org/10.1016/S0040-4020(97)10356-8