Thianthrene 5-oxide as a mechanistic probe for assessing the electronic character of oxygen-transfer agents

Hydrolytic Stability and Hydrogen Peroxide Activation of Zirconium‐Based Oxoclusters

“…Concerning the electronic character of the oxidant species, previous kinetics studies showed that mononuclear d 0 metal peroxide complexes usually behave like electrophilic oxidants,43a,43b and the S ratio is generally much higher than 1, as the rate of sulfide oxidation is up to two orders of magnitude faster than that of the following step 43a,43d,45. In our case, lower S values were generally obtained, and a reversal of reactivity was observed at 50 °C for Zr 12 , for which S became less than 1.…”

Revisiting the Hammett ρ Parameter for the Determination of Philicity: Nucleophilic Substitution with Inverse Charge Interaction

“…As a consequence of their peculiar "ambiphilic" reactivity, sulfoxides are considered unique probes for the description of the oxidant philicity in chemistry and molecular biology. [7] Herein, we decided to tackle the mechanisms of OT investigating theoretically the original studies that are at the base of the interpretation of the ambiphilicity of sulfoxides. This gave us the possibility to reinterpret the original results paving the way for a new description of OT reactivity which extends, and to some extent redefines, the basic concept of nucleophilic substitution and highlights severe limitations on the information which can be gathered from Hammett 1 parameter.…”

Bis(trifluoroacetoxyiodo)benzene-InducedActivation oftert-Butyl Hydroperoxide for the Direct Oxyfunctionalization of Arenes to Quinones

“…The tert-butylperoxy radical has been shown to be an efficient radical oxidant with the highly electrophilic nature for the conversion of sulfides to sulfoxides. 12 Addition of tert-butylperoxy radicals to 4a leads to the intermediary formation of 1,4-bist-butylperoxy-1,4-dihydro-naphthalene, which might constitute one of the possible reaction pathways. To investigate the fate of the tert-butylperoxy groups of 2b, 1 H NMR experiments were carried out in CDCl 3 at room temperature and products were analyzed: Acetone, tertbutyl alcohol and iodo-benzene were detected.…”