Saucy-Marbet Rearrangement

30 October, 2015 / by SK / in Reactions

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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 1958, 41, 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 1967, 50, 1158. DOI: 10.1002/hlca.19670500423
・ Heathcock, C. H.; Henderson, M. A. J. Org. Chem. 1988, 53, 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. 2004, 126, 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. 2007, 46, 7629. DOI:10.1002/anie.200703027
[3] Jeker, O. F.; Carreira, E. M. Angew. Chem. Int. Ed. 2012, 51, 3474. DOI: 10.1002/anie.201109175