Reformatskii reagent

Sato, T., itoh, T., Fujisawa, T. Faciie synthesis of 3-oxo esters by a coupiing reaction of the Reformatskii reagent with acyi chiorides cataiyzed by a paiiadium compiex. Chem. Lett. 1982, 1559-1560. 

Aivernhe, G., Lacombe, S., Laurent, A., Marquet, B. Addition of the Reformatskii reagent to azirines. Synthesis of 4-amino iactones. J. Chem. Res., Synop. 1980, 54-55. 

FIGURE 17.53 Reformatskii reagent considered as an ester enolate. 

A Reformatskii reagent may be regarded as a zinc enolate and is useful for selectivity in cross condensation reactions. 

This is most easily accomplished using a Reformatskii reagent BrZnCFjCOjEt. 

Reformatskii reagents e.g., BrZnCHjCOOEt) and the anion of diethyl malonates are useful equivalents of the anion of ethyl acetate. 

Matsubara, S., Tsuboniwa, N., Morizawa, Y., Oshima, K., Nozaki, H. Reformatskii type reaction with new aluminum reagents containing an aluminum-tin or aluminum-lead linkage. Bull. Chem. Soc. Jpn. 1984, 57, 3242-3246. 

Additive in Various Reduction Systems. TMSCl has been employed in many different reduction systems to improve the reactivity and/or increase the selectivity. The reagent has been used to activate zinc dust or as additive for Reformatskii reactions. While less reactive than Mg/TMSCl combination, the Zn/TMSCl combination proved to be the preferred reagent system for large scale and high concentrated preparation of diamines through the pinacol coupling of two molecules of imines (eq 76). ... 

The Reformatskii reaction involves the reaction of the product of an a-halo ester and activated zinc in the presence of an anhydrous organic solvent, with a carbonyl compound, followed by hydrolysis. The reaction is very similar in nature to the Grignard reaction except the carbonyl reagent is added at the start. It has been suggested that Grignard reactions might be conducted in a similar manner. 

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