Amidine dications as superelectrophiles

Michael J Corr, Mark D Roydhouse, Kirsty F Gibson, Sheng-Ze Zhou, Alan R Kennedy, John A Murphy

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

2-Dimethylalkylammonium pyridinium and 2-dimethylalkylammonium pyrimidinium ditriflate salts are very powerful methylating agents toward phosphorus (triphenylphosphine) and nitrogen (triethylamine) nucleophiles. In competition experiments with triethylamine as nucleophile, these N-methyl disalts are more reactive methylating agents than dimethyl sulfate. Reaction of the pyridinium dications with water as an oxygen nucleophile leads to attack at the 2-position of the heteroaromatic ring and displacement of an ammonium group; 2-hydroxypyridinium compounds are formed in the first instance, which are easily converted to 2-pyridones. Extending the scope of the reactions, a tricationic 2,6-bis(dimethylalkylammonium) pyridinium salt has also been prepared and characterized and its reactivity as a methylating agent assessed in comparison with that of the dications.
Original languageEnglish
Pages (from-to)17980-17985
Number of pages6
JournalJournal of the American Chemical Society
Volume131
Issue number49
DOIs
Publication statusPublished - Nov 2009

Fingerprint

Amidines
Nucleophiles
Salts
Ammonium Compounds
Phosphorus
Nitrogen
Oxygen
Water
triethylamine
Experiments
2-hydroxypyridine
dimethyl sulfate
triphenylphosphine

Keywords

  • methylating agents
  • triethylamine
  • oxygen nucleophile

Cite this

Corr, Michael J ; Roydhouse, Mark D ; Gibson, Kirsty F ; Zhou, Sheng-Ze ; Kennedy, Alan R ; Murphy, John A. / Amidine dications as superelectrophiles. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 49. pp. 17980-17985.
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abstract = "2-Dimethylalkylammonium pyridinium and 2-dimethylalkylammonium pyrimidinium ditriflate salts are very powerful methylating agents toward phosphorus (triphenylphosphine) and nitrogen (triethylamine) nucleophiles. In competition experiments with triethylamine as nucleophile, these N-methyl disalts are more reactive methylating agents than dimethyl sulfate. Reaction of the pyridinium dications with water as an oxygen nucleophile leads to attack at the 2-position of the heteroaromatic ring and displacement of an ammonium group; 2-hydroxypyridinium compounds are formed in the first instance, which are easily converted to 2-pyridones. Extending the scope of the reactions, a tricationic 2,6-bis(dimethylalkylammonium) pyridinium salt has also been prepared and characterized and its reactivity as a methylating agent assessed in comparison with that of the dications.",
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Corr, MJ, Roydhouse, MD, Gibson, KF, Zhou, S-Z, Kennedy, AR & Murphy, JA 2009, 'Amidine dications as superelectrophiles', Journal of the American Chemical Society, vol. 131, no. 49, pp. 17980-17985. https://doi.org/10.1021/ja908191k

Amidine dications as superelectrophiles. / Corr, Michael J; Roydhouse, Mark D; Gibson, Kirsty F; Zhou, Sheng-Ze; Kennedy, Alan R; Murphy, John A.

In: Journal of the American Chemical Society, Vol. 131, No. 49, 11.2009, p. 17980-17985.

Research output: Contribution to journalArticle

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T1 - Amidine dications as superelectrophiles

AU - Corr, Michael J

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AB - 2-Dimethylalkylammonium pyridinium and 2-dimethylalkylammonium pyrimidinium ditriflate salts are very powerful methylating agents toward phosphorus (triphenylphosphine) and nitrogen (triethylamine) nucleophiles. In competition experiments with triethylamine as nucleophile, these N-methyl disalts are more reactive methylating agents than dimethyl sulfate. Reaction of the pyridinium dications with water as an oxygen nucleophile leads to attack at the 2-position of the heteroaromatic ring and displacement of an ammonium group; 2-hydroxypyridinium compounds are formed in the first instance, which are easily converted to 2-pyridones. Extending the scope of the reactions, a tricationic 2,6-bis(dimethylalkylammonium) pyridinium salt has also been prepared and characterized and its reactivity as a methylating agent assessed in comparison with that of the dications.

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