On the fluxional behavior of Dess-Martin periodinane: a DFT and 17O NMR study.
The structure and dynamics of the Dess-Martin periodinane, a I(V) iodobenzene compound widely used in organic synthesis as a mild oxidant, were studied by a combined (17)O NMR and DFT calculations approach. The results show that a degenerate [1,3] sigmatropic shift of iodine between the two oxygen atoms of each of the three acetoxy groups occurs in solution. The energy barrier of this process depends on the position of the acetoxy group with respect to the iodoxolone ring and is much lower than the energy barrier observed for similar I(III) compounds.
Laboratoire de RMN haute résolution CP 160/08, Université Libre de Bruxelles, 50 av. F.-D. Roosevelt, 1050 Brussels, Belgium.
Luca
L
Fusaro
Michel
M
Luhmer
Giovanni
G
Cerioni
Francesca
F
Mocci
D003198:Computer Simulation; D018360:Crystallography, X-Ray; D007462:Iodobenzenes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010103:Oxygen Isotopes; D011789:Quantum Theory
D007462:Iodobenzenes; D010103:Oxygen Isotopes