Dess–Martin periodinane (DMP) oxidation
Alcohols can be oxidized to aldehydes, ketones, and carboxylic acids depending on their structure and the type of oxidizing agent. In general, we can classify oxidizing agents as strong and mild.
Mild oxidizing reagents stop the oxidation of the alcohol once the carbonyl group is formed. And if the alcohol is a primary, the product is an aldehyde, while the oxidation of a secondary alcohol results in a ketone.
The strong oxidizing agents oxidize Primary Alcohols to Carboxylic Acids and Secondary Alcohols to Ketones:
The oxidation of alcohols is covered in more detail in the following post: Oxidation of Alcohols.
The Mechanism of Dess-Martin Oxidation
Dess–Martin periodinane (DMP oxidation) is a selective method for oxidizing primary alcohols to aldehydes.
Another advantage of the DMP oxidation is that it is performed at milder conditions and does not require the presence of strong acids.
The reaction starts with a substitution on the iodine, where the alcohol replaces one of the acetate ions, followed by a deprotonation, which forms an aryliodo(III) ester – periodinane intermediate.
The periodinane intermediate is then transformed to the corresponding carbonyl compound by a possible intramolecular removal of the ɑ-hydrogen to form a C=O π bond.
