Pummerer rearrangement

Thioethers can also be prepared by many other methods, such as the Pummerer rearrangement.

The Pummerer rearrangement in one of its reaction step contains a sulfur variation.

Thionyl chloride can be used in variations of the Pummerer rearrangement.

In this case, the reaction proceeds with Pummerer rearrangement:

The mechanism of the Pummerer rearrangement begins with the acylation of the sulfoxide (1 and 2).

Examples include the Pummerer rearrangement, the Pinnick oxidation and the Birch reduction.

Interestingly, β-ketosulfoxides can also be used in the Pummerer rearrangement to introduce nucleophiles alpha to a carbonyl (5).

The Pummerer rearrangement is an organic reaction whereby an alkyl sulfoxide rearranges to an α-acyloxy-thioether in the presence of acetic anhydride.

The reaction mechanism with DMSO as methylene donor for this reaction is similar to that of the Pummerer rearrangement.

Methyl methanethiosulfinate can also disproportionate to a 1:1 mixture of dimethyl disulfide and methyl methanethiosulfonate (CHSOSCH) and rearrange via a Pummerer rearrangement to CHS(O)CHSSCH).