On the fluxional behavior of Dess-Martin periodinane: a DFT and [super 17]O NMR study

Combined [super 17]O NMR and DFT calculation methods were used to study the structure and dynamics of the Dess-Martin periodinane, a I(V) iodobenzene compound widely used in organic synthesis as a mild oxidant. The results showed that a degenerate [1,3] sigmatropic shift of iodine between the two oxygen atoms of each of the three acetoxy groups took place in solution and the energy barrier of the process depended on the position of the acetoxy group with respect to the iodoxolone ring.