Reductive Eliminations from λ3-lodanes: Understanding Selectivity and the Crucial Role of the Hypervalent Bond

This computational study investigates the factors governing the selectivity of the reductive eliminations from rapidly equilibrating isomeric lambda(3)-iodanes derived from a diaryl iodonium salt and a nucleophile. The chemoselectivity is mainly determined by the partial charge at the ipso-carbon atom involved in the 3-center-4-electron bond.