Parikh–Doering oxidation

The first step of the Parikh–Doering oxidation is the reaction of dimethyl sulfoxide (DMSO), which exists as a hybrid of the resonance structures 1a and 1b, with sulfur trioxide (2), giving intermediate 3. Nucleophilic attack by alcohol 4 and deprotonation by pyridine (5) gives intermediate 6, an alkoxysulfonium ion associated with the anionic pyridinium sulfate complex. The addition of at least two equivalents of base deprotonates the alkoxysulfonium ion to give sulfur ylide 7 and removes the pyridinium sulfate counterion. In the last step, the ylide goes through a five-membered ring transition state to give the desired ketone or aldehyde 8, as well as an equivalent of dimethyl sulfide. ==Application==

Parikh–Doering oxidation is widely applied in organic synthesis. Here is an example of the Parikh–Doering oxidation's application in the Nicolaou cortistatin total synthesis, where the reaction transforms the hydroxyl functional group into an aldehyde. This process leads to Ohira-Bestmann homologation, which is critical in the following 1,4 addition/aldol condensation/dehydration cascade that forms cortistatins' seven-membered ring. The synthetic route is shown below: ==See also==