How does the presence of an electron-withdrawing group (e.g., carboxylate) affect the reaction of arylamines with SeO₂?

Label:chem

Topic
Methyl anthranilate, which has an electron-withdrawing carboxylate group, was studied to understand its reaction with SeO₂. The delocalization of the amine lone pair electrons over the adjacent carboxylate function was expected to influence the reaction pathway.

From: "Competing electrophilic substitution and oxidative polymerization of arylamines with selenium dioxide", Beilstein J. Org. Chem. 2024, 20, 1221–1235.
Answer
Methyl anthranilate underwent significant selenation due to the delocalization of the amine lone pair electrons over the adjacent carboxylate function. This suppressed oxidative polymerization and led to the formation of diaryl selenides (compounds 11 and 12) and oxamide 13. The diaryl selenides were structurally characterized using single-crystal X-ray diffraction.
Conclusion: Electron-withdrawing groups on arylamines suppress oxidative polymerization and favor electrophilic selenation when reacting with SeO₂.
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