Blaise Reaction

E. E. Blaise, Compt. Rend. 132, 478 (1901).

Formation of β-oxoesters by treatment of α-bromocarboxylic esters with zinc in the presence of nitriles. The intermediate organozinc compound reacts with the nitrile and the complex is hydrolyzed with 30% potassium hydroxide:

A. Horeau, J. Jacques, Bull. Soc. Chim. 1947, Mem. 58; J. Cason et al., J. Org. Chem. 18, 1594 (1953); H. Henecka, Houben-Weyl 7/2a, 518 (1973); K. Nützel, ibid. 13/2a, 829. Modified conditions: S. M. Hannick, Y. Kishi, J. Org. Chem. 48, 3833 (1983); N. Zylber et al., J. Organomet. Chem. 444, 1 (1993); K. Narkunan, B.-J. Uang, Synthesis 1998, 1713. Stereoselectivity: J. J. Duffield, A. C. Regan, Tetrahedron: Asymmetry 7, 663 (1996); A. S.-Y. Lee et al., Tetrahedron Lett. 38, 443 (1997); J. Syed et al., Tetrahedron: Asymmetry 9, 805 (1998). Cf. Reformatsky Reaction.