0000000000749450
AUTHOR
Alba Díaz-rodríguez
Oxidation of Sulfides with a Silica-Supported Peracid in Supercritical Carbon Dioxide under Flow Conditions: Tuning Chemoselectivity with Pressure
Supercritical carbon dioxide is a convenient medium for performing the selective oxidation of sulfides 1 to either sulfoxides 2 or sulfones 3 with [2-percarboxyethyl]-functionalized silica (4) under flow conditions. The chemoselectivity of the reaction, which results from the different diffusion rates of sulfide and sulfoxide over the reagent bed, can be controlled by adjusting the pressure and the hydration of the silica surface as both the solvating power of the mobile phase and the surface activity of the stationary phase determine the migration rates of sulfide 1 and sulfoxide 2 over the supported peroxide. The results elucidate the impact of surface phenomena on the course of chemical …
Silver-Catalyzed C-C Bond Formation between Methane and Ethyl Diazoacetate in Supercritical CO2
Even in the context of hydrocarbons’ general resistance to selective functionalization, methane’s volatility and strong bonds pose a particular challenge. We report here that silver complexes bearing perfluorinated indazolylborate ligands catalyze the reaction of methane (CH4) with ethyl diazoacetate (N2CHCO2Et) to yield ethyl propionate (CH3CH2CO2Et). The use of supercritical carbon dioxide (scCO2) as the solvent is key to the reaction’s success. Although the catalyst is only sparingly soluble in CH4/CO2 mixtures, optimized conditions presently result in a 19% yield of ethyl propionate (based on starting quantity of the diazoester) at 40°C over 14 hours.