This is consistent with the shorter I-OTf bond distance within 21_OTf (2.252 Å) in comparison to the equivalent bond in 20 (2.412 Å) (Figure ). It is established that a hypervalent twist must take place for the iodine oxidant to be sufficiently reactive toward the redox process. 9,10 The corresponding twist occurs by overcoming an activation barrier of 8.4 kcal/mol via TS21-22_OTf which forms 22_OTf. The approach of the ortho-carbon of the phenolate to the oxo ligand in 22_OTf promotes the first redox process via an associative mechanism to afford 23_OTf. 10a