Saucy-Marbet Rearrangement

Saucy-Marbet Rearrangement

Overall Score4
  • Generality
  • Reagent Availability
  • Experimental User Friendliness
  • General Characteristics

Propargyl vinyl ethers undergo thermal or catalylzed [3,3]-sigmatropic rearrangement to give the corresponding ketoallenes. For chiral compounds, the stereochemistry of the ether is transferred to the axial chirality of the allene. This reaction is also known as the propargyl Claisen rearrangement.

  • General References

・ Saucy, G.; Chopard-dit-Jean, L. H.; Guex, W.; Ryser, G.; Isler, O. Helv. Chim. Acta 195841, 160. DOI: 10.1002/hlca.660410120
・ Marbet, R.; Saucy, G. Chimia 1960, 14, 361.
・ Black, D. K.; Landor, S. R. J. Chem. Soc. 1965,6784. DOI: 10.1039/JR9650006784
・ Saucy, G.; Marbet, R. Helv. Chim. Acta 196750, 1158. DOI: 10.1002/hlca.19670500423
・ Heathcock, C. H.; Henderson, M. A. J. Org. Chem. 198853, 4736. DOI: 10.1021/jo00255a014
・ Tang, Y.; Shen, L.; Dellaria, B. J.; Hsung, R. P. Tetrahedron Lett. 2008, 6404. doi:10.1016/j.tetlet.2008.08.089
・ Cao, T.; Deitch, J.; Linton ,E. C.; Kozlowski, M. C. Angew. Chem. Int. Ed. 2012, 51, 2448. DOI: 10.1002/anie.201107417

  • Reaction Mechanism

  • Examples

The gold catalyst accelerates the rearrangement.[1]


An impressive example from the synthesis of azadirachtin.[2]


The gold-catalyzed Saucy-Marbet rearrangement was used in the total synthesis of indoxamycin B.[3]


  • Experimental Procedure

  • Experimental Tips

  • References

[1] Sherry, B. D.; Toste, F. D. J. Am. Chem. Soc. 2004126, 15978. DOI: 10.1021/ja044602k
[2] Veitch, G. E.; Beckmann, E.; Burke, B. J.; Boyer, A.; Maslen, S. L.; Ley, S. V. Angew. Chem. Int. Ed. 200746, 7629. DOI:10.1002/anie.200703027
[3] Jeker, O. F.; Carreira, E. M. Angew. Chem. Int. Ed. 201251, 3474. DOI: 10.1002/anie.201109175

  • Related Reactions

  • Related Books

  • External Links

Pericyclic reaction (PDF, Evans Group)
The Saucy-Marbet reaction (NNNS Blog)
Indoxamycin B (Chemistry World)


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