Graham reaction explained

In organic chemistry, the Graham reaction is an oxidation reaction that converts an amidine into a diazirine using a hypohalite reagent. The halide of the hypohalite oxidant, or another similar anionic additive to the reaction, is retained as a substituent on the diazirine product. The reaction was first reported in 1965.^[1] Various reaction mechanisms have been proposed.^{[2] [3]}

Amidine substrates for the reaction can easily be formed from the corresponding nitriles via the Pinner reaction. The halide substituent in the diazirine product can be displaced by a various nucleophiles.^[4]

Notes and References

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