A one-pot, two step synthesis of 2,2-disubstituted 1-nitroalkenes

Yeong Jiunn Jang, Wen-Wei Lin, Yuh Kuo Shih, Ju Tsung Liu, Ming Hsing Hwang, Ching-Fa Yao

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The reactions of ketones 1a-o, nitromethane 2, and a stoichiometric amount of piperidine 3a or ethylenediamine 3b in the presence of mercaptan 6a in THF or CH3CN solution give high yields of β-nitrosulfides 7a-o. The latter can be oxidized by 8a (m-CPBA or m-CPBA/AcOH) at 0°C, 8b (H2O2/AcOH), or 8c (H2O2) at room temperature, thus generating β-nitroalkylsulfoxides 9a-o, which then undergo elimination to produce medium to high yields of 2,2-disubstituted-1-nitroalkenes 5a-o, when refluxed in a solution of ClCH2CH2Cl (1,2-dichloroethane). After preparation from 1a-o, 2, 3, and 6a, 7a-o were oxidized with 8a, 8b, or 8c in a mixture of CH3CN and ClCH2CH2Cl to generate β-nitrosulfoxides 9a-o, which then underwent elimination under refluxing under one-pot conditions. Compounds 14 and 15g were also prepared using 13, 2, 3b, and 6, in a similar manner.

Original languageEnglish
Pages (from-to)4979-4992
Number of pages14
JournalTetrahedron
Volume59
Issue number27
DOIs
Publication statusPublished - 2003 Jun 30

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ethylenediamine
Ketones
Sulfhydryl Compounds
Temperature
3-chloroperbenzoic acid
nitromethane
ethylene dichloride
piperidine

Keywords

  • Hydrogen peroxide
  • Ketone
  • Mercaptan
  • Nitro-olefin
  • One-pot

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

A one-pot, two step synthesis of 2,2-disubstituted 1-nitroalkenes. / Jang, Yeong Jiunn; Lin, Wen-Wei; Shih, Yuh Kuo; Liu, Ju Tsung; Hwang, Ming Hsing; Yao, Ching-Fa.

In: Tetrahedron, Vol. 59, No. 27, 30.06.2003, p. 4979-4992.

Research output: Contribution to journalArticle

Jang, Yeong Jiunn ; Lin, Wen-Wei ; Shih, Yuh Kuo ; Liu, Ju Tsung ; Hwang, Ming Hsing ; Yao, Ching-Fa. / A one-pot, two step synthesis of 2,2-disubstituted 1-nitroalkenes. In: Tetrahedron. 2003 ; Vol. 59, No. 27. pp. 4979-4992.
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