Hydrogen atom abstraction

Hydrogen atom abstraction or hydrogen atom transfer (HAT) in chemistry is any chemical reaction in which a hydrogen free radical is abstracted from a substrate according to the general equation:

X^. + H-Y -> X-H + Y^.

Examples of HAT reactions are oxidative reactions in general, hydrocarbon combustion and reactions involving cytochrome P450 containing an iron(V)-oxo unit. The abstractor is usually a radical species itself. An example of a closed-shell abstractor is chromyl chloride. HAT can take place through proton-coupled electron transfer.[1] A synthetic example is found in iron zeolites, which stabilize Alpha-Oxygen.[2][3]

Non-radical Hydrogen Abstraction

It is reported in literature that during the synthesis of a Coelenterazine derivative, a non-radical hydrogen abstraction was observed on a substituted aminoimidazole in a typical Sandmayer hyroxilation condition.[4]

References

Lai W.; Li C.; Chen H.; Shaik S. (2012). "Hydrogen-Abstraction Reactivity Patterns from A to Y: The Valence Bond Way". Angew. Chem. Int. Ed. 51 (23): 5556–5578. doi:10.1002/anie.201108398. PMID 22566272.
Snyder, Benjamin E. R.; Vanelderen, Pieter; Bols, Max L.; Hallaert, Simon D.; Böttger, Lars H.; Ungur, Liviu; Pierloot, Kristine; Schoonheydt, Robert A.; Sels, Bert F. (August 2016). "The active site of low-temperature methane hydroxylation in iron-containing zeolites". Nature. 536 (7616): 317–321. Bibcode:2016Natur.536..317S. doi:10.1038/nature19059. ISSN 0028-0836. PMID 27535535.
Snyder, Benjamin E. R.; Bols, Max L.; Schoonheydt, Robert A.; Sels, Bert F.; Solomon, Edward I. (2017-12-19). "Iron and Copper Active Sites in Zeolites and Their Correlation to Metalloenzymes". Chemical Reviews. 118 (5): 2718–2768. doi:10.1021/acs.chemrev.7b00344. ISSN 0009-2665. PMID 29256242.
Vece V.; Vuocolo G. (2015). "Multicomponent Synthesis of Novel Coelenterazine Derivatives Substituted at the C-3 Position". Tetrahedron. 71 (46): 8781–8785. doi:10.1016/j.tet.2015.09.048.

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[1] Lai W.; Li C.; Chen H.; Shaik S. (2012). "Hydrogen-Abstraction Reactivity Patterns from A to Y: The Valence Bond Way". Angew. Chem. Int. Ed. 51 (23): 5556–5578. doi:10.1002/anie.201108398. PMID 22566272.

[2] Snyder, Benjamin E. R.; Vanelderen, Pieter; Bols, Max L.; Hallaert, Simon D.; Böttger, Lars H.; Ungur, Liviu; Pierloot, Kristine; Schoonheydt, Robert A.; Sels, Bert F. (August 2016). "The active site of low-temperature methane hydroxylation in iron-containing zeolites". Nature. 536 (7616): 317–321. Bibcode:2016Natur.536..317S. doi:10.1038/nature19059. ISSN 0028-0836. PMID 27535535.

[3] Snyder, Benjamin E. R.; Bols, Max L.; Schoonheydt, Robert A.; Sels, Bert F.; Solomon, Edward I. (2017-12-19). "Iron and Copper Active Sites in Zeolites and Their Correlation to Metalloenzymes". Chemical Reviews. 118 (5): 2718–2768. doi:10.1021/acs.chemrev.7b00344. ISSN 0009-2665. PMID 29256242.

[4] Vece V.; Vuocolo G. (2015). "Multicomponent Synthesis of Novel Coelenterazine Derivatives Substituted at the C-3 Position". Tetrahedron. 71 (46): 8781–8785. doi:10.1016/j.tet.2015.09.048.