Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 82, Issue 11, Pages 5761-5768Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.7b00563
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- Ministero dell'Istruzione, dell'Universita e della Ricerca (MIUR)
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A change in regioselectivity has been observed in the hydtngen:atoin transfer (HAT) reactions from 4-alkyl-N,N-dimethylbenzylamines (alkyl = ethyl, isopropyl, and benzyl) to the plithalimide 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 alpha to nitrogen toward HAT to PINO as evidenced by the 10(4)-10(7)-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.
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