Blaise reaction
From Wikipedia, the free encyclopedia
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] [3] The final intermediate is a metaloimine, which is hydrolyzed to give the desired β-ketoester.[4]
Bulky aliphatic esters tend to give higher yields. Steven Hannick and Yoshito Kishi have developed an improved procedure.[5]
It has been noted [6][7] that free hydroxyl groups can be tolerated in the course of this reaction, which is surprising for reactions of organometal halides.
[edit] 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). (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)
- [8] Marko, I.E. J. Am. Chem. Soc. 2007, ASAP doi:10.1021/ja0691728
- [9] Wang, D.; Yue, J.-M. Synlett 2005, 2077-2079.
