Ireland–Claisen rearrangement explained

The Ireland–Claisen rearrangement is a chemical reaction of an allylic ester with strong base to give an γ,δ-unsaturated carboxylic acid.^{[1] [2] [3]}

Several reviews have been published.^{[4] [5] [6]}

Mechanism

The Ireland–Claisen rearrangement is a type of Claisen rearrangement. The mechanism is therefore a concerted [3,3]-sigmatropic rearrangement which according to the Woodward–Hoffmann rules show a concerted, suprafacial, pericyclic reaction pathway.

See also

• Cope rearrangement
• Overman rearrangement

Notes and References

1. Ireland, R. E. . Mueller, R. H. . . 10.1021/ja00771a062. Claisen rearrangement of allyl esters. 1972. 94. 16. 5897.
2. Ireland, R. E. . Mueller, R. H. . Willard, A. K. . J. Am. Chem. Soc.. 1976. 98. 2868–2877. 10.1021/ja00426a033. The ester enolate Claisen rearrangement. Stereochemical control through stereoselective enolate formation. 10.
3. Catalytic Diastereoselective Reductive Claisen Rearrangement. Miller, S. P. . Morken, J. P.. 10.1021/ol026273b . Organic Letters. 2004. 60. 2743–2745. 16. 12153224.
4. Ziegler, F. E. . Acc. Chem. Res.. 1977. 10. 1423–1452. 10.1021/ar50114a006. Stereo- and regiochemistry of the Claisen rearrangement: Applications to natural products synthesis. 6.
5. Pereira, S.. Srebnik, M.. Aldrichimica Acta. 1993. 26. 1. 17–29. The Ireland–Claisen rearrangement. 2014-01-25. 2014-02-19. https://web.archive.org/web/20140219094411/http://www.sigmaaldrich.com/content/dam/sigma-aldrich/docs/Aldrich/Acta/al_acta_26_01.pdf. dead.
6. Chai, Y. . Hong, S. . Lindsay, H. A. . McFarland, C. . McIntosh, M. C. . Tetrahedron. 2002. 58. 2905–2928. 10.1016/S0040-4020(02)00164-3. New aspects of the Ireland and related Claisen rearrangements. 15.