Reaction Mechanism
The reaction mechanism for an oxidation of an alcohol to an aldehyde according the so-called hypervalent twisting mechanism involves a ligand exchange reaction replacing the hydroxyl group by the alcohol followed by a twist and a elimination reaction. The twist is a requirement because the iodine to oxygen double bond is oriented out of plane with the alkoxy group and the concerted elimination would not be able to take place. This twist reaction is a rearrangement in which the oxygen atom is moved into a proper plane for a 5 membered cyclic transition state in the elimination reaction and is calculated by Computational chemistry to be the rate-determining step in the oxidation. The twist mechanism also explains why oxidation is faster for larger alcohols than for small alcohols. The twist is driven forward by the steric hindrance that exists between the ortho hydrogen atom and the protons from the alkoxy group and larger alkoxy groups create larger steric repulsion. The same computation predicts a much faster reacting IBX derivative with a 100 fold reaction rate when this ortho hydrogen atom is replaced by a methyl group thus facilitating the twist until the elimination reaction takes prevalence as the rate determining step.
IBX exists as two tautomers one of which is the carboxylic acid. The acidity of IBX which has been determined in water (pKa 2.4) and DMSO (pKa 6.65) is known to affect organic reactions, for instance acid-catalyzed isomerization accompanying oxidations.
Read more about this topic: 2-Iodoxybenzoic Acid
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