A new strategy for the synthesis of a-hydroxy ketones by samarium (I1) iodide-mediated threecomponent coupling of organic halides, an isocyanide, and carbonyl compounds is disclosed. An (a-iminoalkyl) samarium (III) species is generated in situ by treatment of an organic halide with 2 equiv of samarium (I1) iodide in the presence of 2, 6-xylyl isocyanide. Subsequent treatment of the mixture with a carbonyl compound affords a-hydroxy imines, ...