Copper-hydroperoxo-mediated N-debenzylation chemistry mimicking aspects of copper monooxygenases.
A substantial oxidative N-debenzylation reaction along with PhCHO formation occurs from a hydroperoxo-copper(II) complex that has a dibenzylamino substrate (N(CH 2Ph) 2 appended as a substituent on one pyridyl group of its tripodal tetradentate TMPA (also TPA, (2-pyridylmethyl)amine)) ligand framework. During the course of the (L (N(CH 2 ) (Ph) 2 ))Cu (II)( (-)OOH) reactivity, the formation of a substrate and a (-)OOH-derived (an oxygen atom) alkoxo Cu (II)( (-)OR) complex occurs. The observation that the same Cu (II)( (-)OR) species occurs from Cu (Iota)/PhIO chemistry suggests the possibility that a copper-oxo (cupryl) reactive intermediate forms during the alkoxo species formation; new ESI-MS data provide further support for this high-valent intermediate. A net H atom abstraction chemistry is proposed on the basis of the kinetic isotope effect studies provided here and the previously published study for a closely related Cu (II)( (-)OOH) species incorporating dimethylamine (N(CH 3) 2) as the internal substrate; the Cu (Iota)/PhIO reactivity with similar isotope effect results provides further support. The reactivity of these chemical systems closely resembles the proposed oxidative N-dealkylation mechanisms that are effected by the copper monooxygenases, dopamine beta-monooxygenase (DbetaM) and peptidylglycine- alpha-hydroxylating monooxygenase (PHM).
Maiti
Debabrata
D
Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.
Narducci Sarjeant
Amy A
AA
Karlin
Kenneth D
KD
D000588:Amines / Q000737:chemistry; D032701:Biomimetics; D003300:Copper / Q000737:chemistry* / Q000378:metabolism; D018360:Crystallography, X-Ray; D015195:Drug Design; D006861:Hydrogen Peroxide / Q000737:chemistry*; D008024:Ligands; D006899:Mixed Function Oxygenases / Q000737:chemistry* / Q000378:metabolism*; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry
D000588:Amines; D008024:Ligands; D011725:Pyridines; D003300:Copper; D006861:Hydrogen Peroxide; D006899:Mixed Function Oxygenases; C023666:pyridine
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