Selective photooxidation of diols with silica bound W10O32 4-

The decatungstate anion W10O32^4^- has been heterogenized on silica previously functionalized with different ammonium cations covalently bound to the surface of the solid support. These materials are investigated as photocatalysts for the oxygen-assisted oxidation of 1,3-butanediol and 1,4-pentanediol. Product distribution and adsorption experiments indicate that the polarity of the environment surrounding the photoactive anion plays a crucial role in controlling the adsorption of diols on the surface and, consequently, their reaction with the photoexcited decatungstate. Proper reaction conditions are found for obtaining more than 90% of 4-hydroxy-2-butanone from 1,3- butanediol and for stopping the oxidation of 1,4-pentanediol to 4-hydroxypentanal with good yield. The employed photocatalysts present a very good stability in repeated experiments.