Predominance of the second cycle in homogeneous Os-catalyzed dihydroxylation: the nature of Os(vi) → Os(viii) reoxidation and unprecedented roles of amine-N-oxides

Our detailed DFT study of Os-catalyzed alkene dihydroxylation revealed that the reaction predominantly proceeds via a second cycle initiated by the formation of a putative Os( viii )trioxoglycolate as a highly reactive intermediate.