ArticleJournal of the American Chemical Society2015
Amine oxidative N-dealkylation via cupric hydroperoxide Cu-OOH homolytic cleavage followed by site-specific fenton chemistry.
Article in Journal of the American Chemical Society, 2015. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 33 papers.
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Who cites it
33 citing papers in PubMed, 117 citations in OpenAlex.
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- Identifying Radical Pathways for Cu(I)/Cu(II) Relay Catalyzed Oxygenation via Online Coupled EPR/UV-Vis/Near-IR Monitoring.Advanced science (Weinheim, Baden-Wurttemberg, Germany) · 2024Article
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- Mapping the Initial Stages of a Protective Pathway that Enhances Catalytic Turnover by a Lytic Polysaccharide Monooxygenase.Journal of the American Chemical Society · 2023Article
- Fenton-like Chemistry by a Copper(I) Complex and HJournal of the American Chemical Society · 2023Article
- Biomass-Derived Single Zn Atom Catalysts: The Multiple Roles of Single Zn Atoms in the Oxidative Cleavage of C-N Bonds.JACS Au · 2023Article
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- Open-Shell Nanosensitizers for Glutathione Responsive Cancer Sonodynamic Therapy.Advanced materials (Deerfield Beach, Fla.) · 2022Article
- De Novo Design of a Self-Assembled Artificial Copper Peptide that Activates and Reduces Peroxide.ACS catalysis · 2021Article
- Mechanistic Study of the Activation and the Electrocatalytic Reduction of Hydrogen Peroxide by Cu-tmpa in Neutral Aqueous Solution.ChemElectroChem · 2021Article
- Visible-light enabled room-temperature dealkylative imidation of secondary and tertiary amines promoted by aerobic ruthenium catalysis.RSC advances · 2021Article
- Palladium-Mediated CAngewandte Chemie (International ed. in English) · 2021Article
- Kinetic analysis of amino acid radicals formed in HProceedings of the National Academy of Sciences of the United States of America · 2020Article
- Mechanistic approaches for chemically modifying the coordination sphere of copper-amyloid-β complexes.Proceedings of the National Academy of Sciences of the United States of America · 2020Article
- A model for gain of function in superoxide dismutase.Biochemistry and biophysics reports · 2020Article
- A merged copper(I/II) cluster isolated from Glaser coupling.Nature communications · 2019Article
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Authors and funding
9 authors at 2 institutions in 1 country.
Funding
Abstract
Copper(II) hydroperoxide species are significant intermediates in processes such as fuel cells and (bio)chemical oxidations, all involving stepwise reduction of molecular oxygen. We previously reported a Cu(II)-OOH species that performs oxidative N-dealkylation on a dibenzylamino group that is appended to the 6-position of a pyridyl donor of a tripodal tetradentate ligand. To obtain insights into the mechanism of this process, reaction kinetics and products were determined employing ligand substrates with various para-substituent dibenzyl pairs (-H,-H; -H,-Cl; -H,-OMe, and -Cl,-OMe), or with partially or fully deuterated dibenzyl N-(CH2Ph)2 moieties. A series of ligand-copper(II) bis-perchlorate complexes were synthesized, characterized, and the X-ray structures of the -H,-OMe analogue were determined. The corresponding metastable Cu(II)-OOH species were generated by addition of H2O2/base in acetone at -90 °C. These convert (t1/2 ≈ 53 s) to oxidatively N-dealkylated products, producing para-substituted benzaldehydes. Based on the experimental observations and supporting DFT calculations, a reaction mechanism involving dibenzylamine H-atom abstraction or electron-transfer oxidation by the Cu(II)-OOH entity could be ruled out. It is concluded that the chemistry proceeds by rate limiting Cu-O homolytic cleavage of the Cu(II)-(OOH) species, followed by site-specific copper Fenton chemistry. As a process of broad interest in copper as well as iron oxidative (bio)chemistries, a detailed computational analysis was performed, indicating that a Cu(I)OOH species undergoes O-O homolytic cleavage to yield a hydroxyl radical and Cu(II)OH rather than heterolytic cleavage to yield water and a Cu(II)-O(•-) species.
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