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36.9.1.8 Method 8: Reactions of Aldehydes/Ketones with α-Halo Ketones (Reformatsky Reaction)

DOI: 10.1055/sos-SD-036-00675

Mahrwald, R.; Schetter, B.Science of Synthesis, (200836944.

The original Reformatsky reaction involves the treatment of an aldehyde or ketone with zinc and an α-halide. The halide is usually an α-bromo ester, vinylogous ester, nitrile, ketone, or amide.[‌564‌] This transformation is very similar to the Grignard reaction,[‌565‌,‌566‌] and is a useful means of synthesizing β-hydroxylated carbonyl compounds. The original reaction has been optimized and this development has been reviewed several times;[‌567‌‌574‌] in addition, there are a number of related methods that use metals other than zinc. High yields are obtained when the Reformatsky reaction and its variations are used with activated zinc,[‌575‌] chromium(II) salts,[‌576‌] indium,[‌577‌] manganese,[‌578‌] low-valent titanium compounds,[‌579‌] samarium(II) iodide,[‌580‌] a combination of cadmium(II) chloride and metallic samarium,[‌581‌] or a combination of bismuth(III) chloride and metallic samarium,[‌582‌] germanium salts,[‌583‌] cobalt catalysts,[‌584‌] rhodium catalysts,[‌585‌] tin compounds,[‌586‌] iron catalysts,[‌587‌] scandium(III) trifluoromethanesulfonate,[‌588‌] and palladium catalysts.[‌589‌] Solid phase reactions are also known,[‌590‌] and even reactions in water are reported.[‌591‌]

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M8 Meeeeeeeee (%) (MMMM) ee (%) Meeeee (%) Mee
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References