We have deconvoluted and established through our DFT studies that a novel F-cation transfer mechanism operates when N-fluoropyridinium salt 1 is used for the efficient synthesis of racemic cis-N-arylaziridines. Even though 1 worked well, we wanted to probe if different halogen sources could mediate alternative reactions via a similar halogen transfer mechanism. Easy-to-handle molecular iodine (I2) is probably the simplest, and one of the cheapest, sources of halogen with an extensive track record of halogen bond catalysis, such as Diels-Alder reaction 9e and Michael addition reaction 11c, 42 . We were intrigued by the possibility that, like F-cation activation, a similar I-cation transfer mechanism could operate in I2 catalyzed reactions. We initiated computational studies, focusing on the I2 catalyzed DA reaction between 1,3-cyclohexadiene 5 and methyl vinyl ketone (MVK, 6) (Figure ). The first study investigated whether molecular iodine could form I-I•••O=C halogen bonds with MVK, and if so, whether these bonds would be activated enough to react with the diene. Whilst the second study probed if the C=C double bond of MVK underwent I-I ••• activation, allowing its subsequent reaction with cyclohexadiene, affording bicyclo[2.2.2]oct-5ene-2-carboxaldehyde 7.