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Revisiting the mechanism of P450 enzymes with the radical clocks norcarane and spiro[2,5]octane.
TLDR
These three structurally similar and functionally simple substrates show a consistent pattern of rearrangement that supports a radical rebound mechanism for this set of cytochrome P450 enzymes. Expand
Remarkable aliphatic hydroxylation by the diiron enzyme toluene 4-monooxygenase in reactions with radical or cation diagnostic probes norcarane, 1,1-dimethylcyclopropane, and 1,1-diethylcyclopropane.
TLDR
The results show a divergence of radical and cation pathways for T4moH-mediated hydroxylation that can be dissected by diagnostic substrate probe rearrangements and by changes in the source of oxygen used for substrate oxygenation. Expand
Copper-based bioinspired oxygenation and glyoxalase-like reactivity.
TLDR
This chemically unprecedented one-pot conversion of acetone to lactate occurs as a multistep process in the gluconeogenic pathway catalyzed by P450 isozyme 3a and Ni- or Zn-based glyoxalases, and an inner-sphere oxidation/isomerization mechanism is proposed. Expand
Synthesis and molecular and solid state structural characterization of mixed CH3–CF3 and CH3–C2F5 fluoroalkyl pyrazoles and a new, TpC2F5,CH3 ligand
Abstract We report a new mixed methyl-fluoroalkyl (Rf) 3,5-substituted pyrazole, Pz R f , CH 3 , with Rf = C2F5. An X-ray structural comparison of Pz R f , CH 3 (Rf = CF3 and C2F5) reveals a similarExpand
Synthesis and molecular structures and oxidation catalysis of mixed alkyl, fluoroalkyl pyrazolylborate metal complexes
Abstract First row transition metal complexes of partly fluorinated tris- and bispyrazolylborate complexes are synthesized and structurally characterized. Both the red cobalt complex,Expand