Nitrogen radical cations

Photoinduced oxidation of amines leads to the formation of amine radical cations. These intermediates display both radical and cationic character with the N-H protons of the primary and secondary amine cation radicals being acidic. As a result, an efficient deprotonation occurs at the carbon a to the nitrogen radical cation giving aminyl radicals (Eq. (3)) [100]. 

Support for a nitrogen radical cation mechanism in P450-catalyzed A-dealkylation reactions... 

Figure 6.13. Probes designed to investigate whether a nitrogen radical cation is involved in P450-catalyzed A -dealkylation reactions.

Fig. 4.18 An alternative meehanism is available for hydroxylation of a earbon adjaeent to a nitrogen atom. This meehanism is initiated by eleetron transfer fiom the nitrogen to compound I, forming a nitrogen radical cation and compound II. Proton removal and recombination with the iron-bound hydroxyl of compound II then yields the hydroxylated product. The high electronegativity of the...

Fig. 4.19 Although a nitrogen radical cation can be detected by rearrangements of cyclopropylamine probes in reactions with horseradish peroxidase (HRP), similar re-...

Fig. 4.21 Optimal alignment for hydrogen abstraction by the P450 ferryl species occurs when the hydrogen to be abstracted is aUgned with the orbital holding the election pair in the neutral nitrogen or the unpaired electron in the nitrogen radical cation...

Maity S, Zheng N (2012) A photo touch on amines new synthetic adventures of nitrogen radical cations. Synlett 23 1851-1856... 

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