Synthesis of (E)-2-(1-ferrocenylmethylidene)malonic acid derivatives by a cobalt-catalyzed domino reaction of ethyl diazoacetate, carbon monoxide and ferrocenylimines

János Balogh, Tamás Kégl, László Párkányi, László Kollár, Ferenc Ungváry, Rita Skoda-Földes

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The domino reaction of ethyl diazoacetate, carbon monoxide and ferrocenylimines was investigated in the presence of Co2(CO) 8 as catalyst. In most cases the main products are 2-(1-ferrocenylmethylidene) malonates formed by an N(1)-C(4) cleavage of the primarily derived β-lactams. The latter compounds could only be isolated when the reaction was carried out at relatively low CO pressure, using an excess of ethyl diazoacetate. trans-N-(tert-Butyl)-3-ethoxycarbonyl-4-ferrocenyl- β-lactam proved to be the most stable one among these compounds and could be isolated in 55% yield. N-alkyl β-lactams were shown to undergo acidic cleavage leading to the E isomers of 2-(1-ferrocenylmethylidene) malonates as the main products. The structures of the two new compounds, (E)-2- ethoxycarbonyl-3-ferrocenyl-N-((R)-1-phenylethyl)-2-propenamide and trans-N-(tert-butyl)-3-ethoxycarbonyl-4-ferrocenyl-β-lactam were confirmed by X-ray crystallography. The relative thermodynamical stability of the products as well as the energetics of the acid-mediated cleavage of the β-lactam ring was elucidated with DFT calculations.

Original languageEnglish
Pages (from-to)1394-1403
Number of pages10
JournalJournal of Organometallic Chemistry
Volume696
Issue number7
DOIs
Publication statusPublished - 1 Apr 2011
Externally publishedYes

Fingerprint

Lactams
Carbon Monoxide
Cobalt
Carbon monoxide
carbon monoxide
cleavage
cobalt
Derivatives
Malonates
acids
Acids
synthesis
products
crystallography
isomers
low pressure
X ray crystallography
X Ray Crystallography
catalysts
Discrete Fourier transforms

Keywords

  • Carbonylation
  • Cobalt-catalysis
  • Domino reactions
  • β-Lactams

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Biochemistry

Cite this

Synthesis of (E)-2-(1-ferrocenylmethylidene)malonic acid derivatives by a cobalt-catalyzed domino reaction of ethyl diazoacetate, carbon monoxide and ferrocenylimines. / Balogh, János; Kégl, Tamás; Párkányi, László; Kollár, László; Ungváry, Ferenc; Skoda-Földes, Rita.

In: Journal of Organometallic Chemistry, Vol. 696, No. 7, 01.04.2011, p. 1394-1403.

Research output: Contribution to journalArticle

Balogh, János ; Kégl, Tamás ; Párkányi, László ; Kollár, László ; Ungváry, Ferenc ; Skoda-Földes, Rita. / Synthesis of (E)-2-(1-ferrocenylmethylidene)malonic acid derivatives by a cobalt-catalyzed domino reaction of ethyl diazoacetate, carbon monoxide and ferrocenylimines. In: Journal of Organometallic Chemistry. 2011 ; Vol. 696, No. 7. pp. 1394-1403.
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AU - Ungváry, Ferenc

AU - Skoda-Földes, Rita

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AB - The domino reaction of ethyl diazoacetate, carbon monoxide and ferrocenylimines was investigated in the presence of Co2(CO) 8 as catalyst. In most cases the main products are 2-(1-ferrocenylmethylidene) malonates formed by an N(1)-C(4) cleavage of the primarily derived β-lactams. The latter compounds could only be isolated when the reaction was carried out at relatively low CO pressure, using an excess of ethyl diazoacetate. trans-N-(tert-Butyl)-3-ethoxycarbonyl-4-ferrocenyl- β-lactam proved to be the most stable one among these compounds and could be isolated in 55% yield. N-alkyl β-lactams were shown to undergo acidic cleavage leading to the E isomers of 2-(1-ferrocenylmethylidene) malonates as the main products. The structures of the two new compounds, (E)-2- ethoxycarbonyl-3-ferrocenyl-N-((R)-1-phenylethyl)-2-propenamide and trans-N-(tert-butyl)-3-ethoxycarbonyl-4-ferrocenyl-β-lactam were confirmed by X-ray crystallography. The relative thermodynamical stability of the products as well as the energetics of the acid-mediated cleavage of the β-lactam ring was elucidated with DFT calculations.

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