New ferrocenyl-substituted heterocycles. Formation under Biginelli conditions, DFT modelling, and structure determination

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Abstract

A series of novel ferrocene-containing-dihydropyrimidines (DHPs) were prepared by three-component Biginelli reactions of formylferrocene, 1,3-dioxo-components and thiourea catalyzed by boric acid and ytterbium triflate, respectively. When cyclic-1,3-diones were employed as dioxo component in the reactions promoted by boric acid, besides one expected 4-ferrocenyl-2-thioxoquinazoline, 9-ferrocenyl-2H-xanthene-1,8-dione and 9-ferrocenylcyclopenta[b]chromen-8-ones could also be isolated as products. By means of control reactions and B3LYP/6-31 G(d) modelling the formation of the chromenone was interpreted by hetero-Diels-Alder addition involving the Knoevenagel intermediate and the cyclopentadiene resulted in situ from acid-catalyzed decomposition of formylferrocene. The enhanced tendency of the acyclic dioxo components to undergo Biginelli reaction avoiding cycloaddition was reasoned by the formation of Knoevenagel intermediates capable of chelating proton or Lewis acids. The structures of the new compounds were established by IR and NMR spectroscopy, including HMQC, HMBC, DEPT and DNOE measurements. Some structural characteristics were disclosed by B3LYP/6-31 G(d) method. Novel ferrocenyl-2-thioxo-dihydropyrimi-dines, and condensed heterocycles were formed in the Biginelli reactions of formylferrocene, 1,3-dioxo-components and thiourea catalyzed by boric acid and ytterbium triflate, respectively. The interpretation of reactions were supported by B3LYP/6-31 G(d) modelling studies. The structures of the new compounds were established by IR and NMR spectroscopy.

Original languageEnglish
Pages (from-to)1852-1857
Number of pages6
JournalJournal of Organometallic Chemistry
Volume695
Issue number15-16
DOIs
Publication statusPublished - 2010

Fingerprint

Boric acid
Ytterbium
Discrete Fourier transforms
Thiourea
Thioureas
boric acids
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
Magnetic Resonance Spectroscopy
Xanthenes
thioureas
Cyclopentanes
Dione
Lewis Acids
ytterbium
Cycloaddition
Acids
Cycloaddition Reaction
Chelation
Protons

Keywords

  • Biginelli reaction
  • DFT calculations
  • Diels-Alder addition
  • Ferrocene
  • NMR spectroscopy

ASJC Scopus subject areas

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

Cite this

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title = "New ferrocenyl-substituted heterocycles. Formation under Biginelli conditions, DFT modelling, and structure determination",
abstract = "A series of novel ferrocene-containing-dihydropyrimidines (DHPs) were prepared by three-component Biginelli reactions of formylferrocene, 1,3-dioxo-components and thiourea catalyzed by boric acid and ytterbium triflate, respectively. When cyclic-1,3-diones were employed as dioxo component in the reactions promoted by boric acid, besides one expected 4-ferrocenyl-2-thioxoquinazoline, 9-ferrocenyl-2H-xanthene-1,8-dione and 9-ferrocenylcyclopenta[b]chromen-8-ones could also be isolated as products. By means of control reactions and B3LYP/6-31 G(d) modelling the formation of the chromenone was interpreted by hetero-Diels-Alder addition involving the Knoevenagel intermediate and the cyclopentadiene resulted in situ from acid-catalyzed decomposition of formylferrocene. The enhanced tendency of the acyclic dioxo components to undergo Biginelli reaction avoiding cycloaddition was reasoned by the formation of Knoevenagel intermediates capable of chelating proton or Lewis acids. The structures of the new compounds were established by IR and NMR spectroscopy, including HMQC, HMBC, DEPT and DNOE measurements. Some structural characteristics were disclosed by B3LYP/6-31 G(d) method. Novel ferrocenyl-2-thioxo-dihydropyrimi-dines, and condensed heterocycles were formed in the Biginelli reactions of formylferrocene, 1,3-dioxo-components and thiourea catalyzed by boric acid and ytterbium triflate, respectively. The interpretation of reactions were supported by B3LYP/6-31 G(d) modelling studies. The structures of the new compounds were established by IR and NMR spectroscopy.",
keywords = "Biginelli reaction, DFT calculations, Diels-Alder addition, Ferrocene, NMR spectroscopy",
author = "K. Kiss and A. Cs{\'a}mpai and P. Soh{\'a}r",
year = "2010",
doi = "10.1016/j.jorganchem.2010.04.036",
language = "English",
volume = "695",
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journal = "Journal of Organometallic Chemistry",
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TY - JOUR

T1 - New ferrocenyl-substituted heterocycles. Formation under Biginelli conditions, DFT modelling, and structure determination

AU - Kiss, K.

AU - Csámpai, A.

AU - Sohár, P.

PY - 2010

Y1 - 2010

N2 - A series of novel ferrocene-containing-dihydropyrimidines (DHPs) were prepared by three-component Biginelli reactions of formylferrocene, 1,3-dioxo-components and thiourea catalyzed by boric acid and ytterbium triflate, respectively. When cyclic-1,3-diones were employed as dioxo component in the reactions promoted by boric acid, besides one expected 4-ferrocenyl-2-thioxoquinazoline, 9-ferrocenyl-2H-xanthene-1,8-dione and 9-ferrocenylcyclopenta[b]chromen-8-ones could also be isolated as products. By means of control reactions and B3LYP/6-31 G(d) modelling the formation of the chromenone was interpreted by hetero-Diels-Alder addition involving the Knoevenagel intermediate and the cyclopentadiene resulted in situ from acid-catalyzed decomposition of formylferrocene. The enhanced tendency of the acyclic dioxo components to undergo Biginelli reaction avoiding cycloaddition was reasoned by the formation of Knoevenagel intermediates capable of chelating proton or Lewis acids. The structures of the new compounds were established by IR and NMR spectroscopy, including HMQC, HMBC, DEPT and DNOE measurements. Some structural characteristics were disclosed by B3LYP/6-31 G(d) method. Novel ferrocenyl-2-thioxo-dihydropyrimi-dines, and condensed heterocycles were formed in the Biginelli reactions of formylferrocene, 1,3-dioxo-components and thiourea catalyzed by boric acid and ytterbium triflate, respectively. The interpretation of reactions were supported by B3LYP/6-31 G(d) modelling studies. The structures of the new compounds were established by IR and NMR spectroscopy.

AB - A series of novel ferrocene-containing-dihydropyrimidines (DHPs) were prepared by three-component Biginelli reactions of formylferrocene, 1,3-dioxo-components and thiourea catalyzed by boric acid and ytterbium triflate, respectively. When cyclic-1,3-diones were employed as dioxo component in the reactions promoted by boric acid, besides one expected 4-ferrocenyl-2-thioxoquinazoline, 9-ferrocenyl-2H-xanthene-1,8-dione and 9-ferrocenylcyclopenta[b]chromen-8-ones could also be isolated as products. By means of control reactions and B3LYP/6-31 G(d) modelling the formation of the chromenone was interpreted by hetero-Diels-Alder addition involving the Knoevenagel intermediate and the cyclopentadiene resulted in situ from acid-catalyzed decomposition of formylferrocene. The enhanced tendency of the acyclic dioxo components to undergo Biginelli reaction avoiding cycloaddition was reasoned by the formation of Knoevenagel intermediates capable of chelating proton or Lewis acids. The structures of the new compounds were established by IR and NMR spectroscopy, including HMQC, HMBC, DEPT and DNOE measurements. Some structural characteristics were disclosed by B3LYP/6-31 G(d) method. Novel ferrocenyl-2-thioxo-dihydropyrimi-dines, and condensed heterocycles were formed in the Biginelli reactions of formylferrocene, 1,3-dioxo-components and thiourea catalyzed by boric acid and ytterbium triflate, respectively. The interpretation of reactions were supported by B3LYP/6-31 G(d) modelling studies. The structures of the new compounds were established by IR and NMR spectroscopy.

KW - Biginelli reaction

KW - DFT calculations

KW - Diels-Alder addition

KW - Ferrocene

KW - NMR spectroscopy

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