A kinetic investigation, supported by theoretical calculations, of steric and ring strain effects on the oxidation of sulfides and sulfoxides by dimethyldioxirane in acetone

Efficient and selective oxidation of sulfides in batch and continuous flow using styrene-based polymer immobilised ionic liquid phase supported peroxotungstates

“…As sulfones are a useful class of compound the conversion-selectivity profile was also monitored as a function of temperature, with a peroxide to substrate ratio of 2.5, in order to identify conditions for the selective formation of methyl phenyl sulfone. Figure 2 shows that sulfoxide selectivity drops dramatically with increased temperature such that sulfone was obtained as the major product in 93% selectivity after 15 min at 328 K. A control reaction for the oxidation of thioanisole conducted in ethanol in the absence of peroxotungstate but with 0.5 mol% 2a and 2.5 equivalents of H2O2 gave no conversion, which confirmed the active role of the catalyst (entry 11).…”

“…3 Sulfoxidation is also the basis for the catalytic oxidative desulfurisation of crude oil to remove sulfur-based impurities as the resulting sulfones can be selectively extracted into a polar solvent under milder conditions than those traditionally required for industrial catalytic hydrodesulfurisation. 4 A variety of powerful oxidants have been employed for sulfoxidation including mchloroperbenzoic acid, 5 UHP, 6 NaClO, 7 NaIO4, 8 oxone 9 KMnO4 10 and dimethyldioxirane 11 , however, these systems often suffer from low activity and/or selectivity, poor thermal stability, protocols that require long reaction times and/or complex handling procedures as well as poor E-factors. 12 As such there has been considerable interest in developing systems that utilise hydrogen peroxide as the oxidant as it is economical, environmentally benign and readily available.…”

Nucleophilic substitution reactions of cyclic thiosulfinates are accelerated by hyperconjugative interactions

“…The reaction energies of these series follow a similar trend to cycloalkanes in which (3-4)a and (3-4)b are signicantly strained, (5-7)a and (5-7)b are relatively unstrained, and (8-10) a and (8-10)b are moderately strained. [20][21][22] The longer S 1 -S 2 bond in the thiacycles relieves some strain compared the corresponding cycloalkanes (e.g., 1,2-dithiolane vs. cyclopentane).…”

Schiff base complex conjugates of bovine serum albumin as artificial metalloenzymes for eco-friendly enantioselective sulfoxidation

“…54 Sulfoxidation is generally achieved using oxidizing agents such as m-chloroperbenzoic acid, 55,56 cumene hydroperoxide (CHP), 57 NaClO, 58 NaIO 4 , 59 oxone, 60 KMnO 4 (ref. 61) and dimethyldioxirane. 62 Many of these oxidants are known to have undesirable characteristics that include toxicity, formation of by-products, extended reaction times, and low yields.…”