Pummerer rearrangement
Pummerer rearrangement | |
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Named after | Rudolph Pummerer |
Reaction type | Rearrangement reaction |
Identifiers | |
RSC ontology ID | RXNO:0000220 |
The Pummerer rearrangement is an
The stoichiometry of the reaction is:
- RS(O)CHR'2 + Ac2O → RSC(OAc)R'2 + AcOH
Synthetic implementation
Aside from acetic anhydride, trifluoroacetic anhydride and trifluoromethanesulfonic anhydride have been employed as activators.[4] Common nucleophiles besides acetates are arenes, alkenes, amides, and phenols.
The usage of α-acyl sulfoxides and
Thionyl chloride can be used in place of acetic anhydride to trigger the elimination for forming the electrophilic intermediate and supplying chloride as the nucleophile to give an α-chloro-thioether:[6]
Other
Mechanism
The mechanism of the Pummerer rearrangement begins with the
The activated thial electrophile can be trapped by various intramolecular and intermolecular nucleophiles to form carbon–carbon bonds and carbon–heteroatom bonds.
The intermediate is so electrophilic that even neutral nucleophiles can be used, including
It is possible to perform the rearrangement using selenium in the place of sulfur.[9]
Pummerer fragmentation
When a substituent on the α position can form a stable carbocation, this group rather than the α-hydrogen atom will eliminate in the intermediate step. This variation is called a Pummerer fragmentation.[10] This reaction type is demonstrated below with a set of sulfoxides and trifluoroacetic anhydride (TFAA):
The organic group "R2" shown in the diagram above on the bottom right is the methyl violet carbocation, whose pKR+ of 9.4 is not sufficient to out-compete loss of H+ and therefore a classical Pummerer rearrangement occurs. The reaction on the left is a fragmentation because the leaving group with pKR+ = 23.7 is particularly stable.
History
The reaction was discovered by Rudolf Pummerer , who reported it in 1909.[11][12]
See also
- Organosulfur chemistry
- Polonovski reaction― similar reaction involving an amine oxide
- Boekelheide reaction ― similar reaction involving a pyridine oxide