Reactivity Patterns of (Protonated) Compound II and Compound I of Cytochrome P450: Which is the better oxidant?

摘要: The cytochromes P450 are versatile enzymes in human physiology that perform substrate hydroxylation reactions extremely efficiently. In this work, we present results of a computational study on the reactivity patterns Compound I, II, and protonated II with model substrates, address question which these compounds is most effective oxidant? All calculations, regardless substrate, implicated I superior oxidant three. However, were found to react free energies activation only few kcal mol-1 higher energy than those obtained I. Therefore, should be able aliphatic groups moderate C-H bond strengths. We have analysed all detail given electronic, thermochemical, valence bond, molecular orbital rationalizations differences explained experimental product distributions. Overall, findings implied alternative oxidants could operate alongside complex reaction mechanisms enzymatic synthetic iron porphyrinoid complexes.