Pummerer Rearrangement: Mechanism, Applications Examples

What is Pummerer Rearrangement explain?

the Pummerer rearrangement is referred for Formation of α-substituted sulfides from the corresponding sulfoxides (must have at least one hydrogen atom at their α-position).

Pummerer Rearrangement Mechanism :

• steps 1: acylation of the sulfoxide oxygen to form an acyloxysulfonium salt
• steps 2 :loss of a proton from the α-carbon to afford an acylsulfonium ylide
• steps 3: cleavage of the sulfur-oxygen bond to give sulfur-substituted carbocation (RDS)
• steps 4: capture of the nucleophile by the carbocation.

Related Reactions:

1. Sommelet-Hauser Rearrangement
2. Willgerodt Rearrangement
3. Payne Rearrangement
4. Curtius Rearrangement
5. Polonovski Rearrangement
6. Smiles Rearrangement

References:

1. de Lucchi, Ottorino; Miotti, Umberto; Modena, Giorgio (1991). The Pummerer Reaction of Sulfinyl Compounds. Organic Reactions. Vol. 40. pp. 157–184. doi:10.1002/0471264180.or040.03. ISBN 978-0471264187.
2. Padwa, Albert; Gunn, David E., Jr.; Osterhout, Martin H. (1997). “Application of the Pummerer Reaction Toward the Synthesis of Complex Carbocycles and Heterocycles”. Synthesis. 1997 (12): 1353–1377. doi:10.1055/s-1997-1384.
3. Smith, Laura H. S.; Coote, Susannah C.; Sneddon, Helen F.; Procter, David J. (2010). “Beyond the Pummerer Reaction: Recent Developments in Thionium Ion Chemistry”. Angewandte Chemie International Edition. 49 (34): 5832–44. doi:10.1002/anie.201000517. PMID 20583014.

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