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. © 2017 American Chemical Society.

Aerobic oxidation of 4-Alkyl-N,N-dimethylbenzylamines catalyzed by N-hydroxyphthalimide: Protonation-Driven control over regioselectivity / Bietti, Massimo; Lanzalunga, Osvaldo; Lapi, Andrea; Martin, Teo; Mazzonna, Marco; Polin, Mariangela; Salamone, Michela. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 1520-6904. - STAMPA. - 82:11(2017), pp. 5761-5768. [10.1021/acs.joc.7b00563]

Aerobic oxidation of 4-Alkyl-N,N-dimethylbenzylamines catalyzed by N-hydroxyphthalimide: Protonation-Driven control over regioselectivity

Bietti, Massimo;Lanzalunga, Osvaldo;Lapi, Andrea;Martin, Teo;Mazzonna, Marco;Salamone, Michela
2017

Abstract

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. © 2017 American Chemical Society.
c-h bonds; hydrogen-atom transfer; oxyl radical pino; stacking interactions; substituted toluenes; aromatic-aldehydes; activated phenols; mild conditions; acetic-acid; abstraction
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Aerobic oxidation of 4-Alkyl-N,N-dimethylbenzylamines catalyzed by N-hydroxyphthalimide: Protonation-Driven control over regioselectivity / Bietti, Massimo; Lanzalunga, Osvaldo; Lapi, Andrea; Martin, Teo; Mazzonna, Marco; Polin, Mariangela; Salamone, Michela. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 1520-6904. - STAMPA. - 82:11(2017), pp. 5761-5768. [10.1021/acs.joc.7b00563]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/963317
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