Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Aerobic Oxidation of 4-Alkyl-N,N-dimethylbenzylamines Catalyzed by N-Hydroxyphthalimide: Protonation-Driven Control over Regioselectivity

Aerobic Oxidation of 4-Alkyl-N,N-dimethylbenzylamines Catalyzed by N-Hydroxyphthalimide: Protonation-Driven Control over Regioselectivity
Marco Mazzonna, Michela Salamone, Teo Martin, Massimo Bietti, Osvaldo Lanzalunga, Andrea Lapi, Mariangela Polin
A change in regioselectivity has been observed in the hydrogen atom transfer (HAT) reactions from 4-alkyl-N,N-dimethylbenzylamines (alkyl = ethyl, isopropyl, and benzyl) to the phthalimide N-oxyl radical (PINO) by effect of protonation. This result can be rationalized on the basis of an acid-induced deactivation of the C–H bonds α to nitrogen toward HAT to PINO as evidenced by the 104–107-fold decrease in the HAT rate constants in acetonitrile following addition of 0.1 M HClO4. This acid-induced change in regioselectivity has been successfully applied for selective functionalization of the less activated benzylic C–H bonds para to the CH2N(CH3)2 group in the aerobic oxidation of 4-alkyl-N,N-dimethylbenzylamines catalyzed by N-hydroxyphthalimide in acetic acid.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00563

DOI: 10.1021/acs.joc.7b00563

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