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.Ref|Blaise1901 Ref|OS1955 Ref|Rao2008 The final intermediate is a metaloimine, which is hydrolyzed to give the desired β-ketoester.Ref|Cason1953

Bulky aliphatic esters tend to give higher yields. Hannick and Kishi have developed an improved procedure.Ref|Hannick1983

It has been noted Ref|Hannick1983Ref|Wang2005 that free hydroxyl groups can be tolerated in the course of this reaction, which is surprising for reactions of organometal halides.

References

# Edmond E. Blaise; "Compt. Rend." 1901, "132", 478.
# Rinehart, K. L., Jr. "Organic Syntheses", Coll. Vol. 4, p.120 (1963); Vol. 35, p.15 (1955). ( [http://www.orgsyn.org/orgsyn/prep.asp?prep=cv4p0120 Article] )
# Rao, H. S. P.; Rafi, S.; Padmavathy, K. "Tetrahedron" 2008, "64", 8037-8043. (Review)
# Cason, J.; Rinehart, K. L., Jr.; Thorston, S. D., Jr. "J. Org. Chem." 1953, "18", 1594. (DOI|10.1021/jo50017a022)
# Hannick, S. M.; Kishi, Y. "J. Org. Chem." 1983, "48", 3833. (DOI|10.1021/jo00169a053)
# Marko, I.E. "J. Am. Chem. Soc." 2007, ASAP DOI|10.1021/ja0691728
# Wang, D.; Yue, J.-M. "Synlett" 2005, 2077-2079.

ee also

*Blaise ketone synthesis
*Reformatsky reaction