ABSTRACT
4-Nitrophenylacetylene-functionalized Cu2O rhombic dodecahedra and cubes have been used to photocatalyze aryl sulfide oxidation generating aryl sulfoxides. With an oxygen supply and light from a blue light-emitting diode (LED), the reaction can be completed in 12 h with a water and methanol mixed solution. Generally high product yields and excellent product selectivity of sulfoxides over sulfones were achieved. In particular, a thioanisole to methyl phenyl sulfoxide yield of 98% was obtained. A mechanistic study has revealed that photogenerated electrons, holes, and superoxide radicals are involved in the oxidation reaction. The benefit of simple photocatalyst preparation and molecular functionalization to boost catalytic performance shows that surface-controlled ionic solids can be very effective photocatalysts for some organic transformations.
ABSTRACT
A facile and efficient synthetic methodology for preparing dibenzosuberones via a C-H bond activation strategy is presented. The ortho-aroylated 3,5-diarylisoxazole was employed as the starting substrate to undergo palladium-catalyzed intramolecular C-H/C-Br bond cross-coupling to produce a variety of dibenzosuberones bearing an isoxazole group in 24 to >99% 1H NMR yields. The dibenzosuberone structure was further confirmed by X-ray crystallography. The developed methodology exhibits very good functional group tolerance. In addition, a rational mechanism was presented for describing the reaction process. For the prepared dibenzosuberone, the use of Mo(CO)6 as the catalyst can easily transform the isoxazole ring into the ß-aminoenone group. Finally, the structure of the anticipated ring-opening product, dibenzosuberenone, bearing a ß-amino-α-ketone group was secured by X-ray crystallography.
