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Graham reaction

From Wikipedia, the free encyclopedia
Oxidation reaction in organic chemistry

Inorganic chemistry, theGraham reaction is anoxidation reaction that converts anamidine into adiazirine using ahypohalite reagent. Thehalide of the hypohalite oxidant, or another similaranionic additive to the reaction, is retained as asubstituent on the diazirine product. The reaction was first reported in 1965.[1] Variousreaction mechanisms have been proposed.[2][3]

Amidine substrates for the reaction can easily be formed from the correspondingnitriles via thePinner reaction. The halide substituent in the diazirine product can be displaced by a variousnucleophiles.[4]

References

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  1. ^Graham, W. H. (1965-10-01). "The Halogenation of Amidines. I. Synthesis of 3-Halo- and Other Negatively Substituted Diazirines".Journal of the American Chemical Society.87 (19):4396–4397.doi:10.1021/ja00947a040.ISSN 0002-7863.
  2. ^Rzepa, Henry (February 18, 2019)."The Graham reaction: Deciding upon a reasonable mechanism and curly arrow representation".
  3. ^Moss, Robert A.; Wlostowska, Joanna; Guo, Wenjeng; Fedorynski, Michal; Springer, James P.; Hirshfield, Jordan M. (1981). "Mechanism of Graham's reaction".J. Org. Chem.46 (24):5048–5050.doi:10.1021/jo00337a061.
  4. ^Moss, Robert A. (2006-02-09). "Diazirines: Carbene Precursors Par Excellence".Accounts of Chemical Research.39 (4):267–272.doi:10.1021/ar050155h.ISSN 0001-4842.PMID 16618094.
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