Blaise reaction

The Blaise reaction is an organic reaction that forms a β-ketoester from the reaction of zinc metal with a α-bromoester and a nitrile.^{[1] [2]} The final intermediate is a metaloimine, which is hydrolyzed to give the desired β-ketoester.^[3]

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Bulky aliphatic esters tend to give higher yields. Hannick and Kishi have developed an improved procedure.^[4]

It has been noted ^[5][6] that free hydroxyl groups can be tolerated in the course of this reaction, which is surprising for reactions of organometal halides.

References

1. ^  Blaise, E. E.; Compt. Rend. 1901, 132, 478.
2. ^  Rinehart, K. L., Jr. Organic Syntheses, Coll. Vol. 4, p.120 (1963); Vol. 35, p.15 (1955). (Article)
3. ^  Cason, J.; Rinehart, K. L., Jr.; Thorston, S. D., Jr. J. Org. Chem. 1953, 18, 1594. (doi:10.1021/jo50017a022)
4. ^  Hannick, S. M.; Kishi, Y. J. Org. Chem. 1983, 48, 3833. (doi:10.1021/jo00169a053)
5. ^[7] Marko, I.E. J. Am. Chem. Soc. 2007, ASAP doi:10.1021/ja0691728
6. ^[8] Wang, D.; Yue, J.-M. Synlett 2005, 2077-2079.

See also

• Blaise ketone synthesis
• Reformatsky reaction