We report an innovative approach for the selective synthesis of polyfunctional derivatives by cross-combination of different radicals generated under mild conditions. The coordinating effect of Ti (IV) plays a key role in the reaction mechanism: due to its chelating action on the hydroxyl groups, it promotes the homolytic C− C bond cleavage of α, β-dihydroxy ketones by enhancing the captodative effect and the consequent stabilization of the corresponding α- ...