Bimodal Evans−Polanyi Relationships in Dioxirane Oxidations of sp3 C−H: Non-perfect Synchronization in Generation of Delocalized Radical Intermediates
The selectivities in C–H oxidations of a variety of compounds by DMDO have been explored with density functional theory. There is a linear Evans–Polanyi-type correlation for saturated substrates. Activation energies correlate with reaction energies or, equivalently, BDEs (ΔH‡sat = 0.91*BDE – 67.8). Unsaturated compounds, such as alkenes, aromatics, and carbonyls, exhibit a different correlation f...