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

Research output: Contribution to journalArticle

44 Citations (Scopus)

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

    Fingerprint

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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