Acid-catalyzed isomerization of pivalaldehyde to methyl isopropyl ketone via a reactive protosolvated carboxonium ion intermediate.

Quantitative rearrangement of pivalaldehyde to methyl isopropyl ketone is observed in acids such as trifluoromethanesulfonic acid, anhydrous HF, and trifluoroethyl alcohol-BF3 but not in trifluoroacetic acid. Studies in a mixture of trifluoroacetic acid and trifluoromethanesulfonic acid show that acids with H(o) < or = -11 are able to carry out complete isomerization. These results and density functional theory calculations at the B3LYP/6-31G level suggest that protonated pivalaldehyde undergoes further protosolvation at higher acidities to a reactive superelectrophilic species resulting in rearrangement. A mechanism for the pivalaldehyde rearrangement to methyl isopropyl ketone in strong protic acids involving a reactive protosolvated superelectrophilic intermediate is suggested. Aspects of the related mechanism of the reaction with isobutane with CO in HF/BF3 medium leading to methyl isopropyl ketone are also discussed.