Serendipity strikes again--efficient preparation of lithium tetramethylcuprate(III) via rapid injection NMR.

Lithium tetramethylcuprate(III), Me(4)CuLi, the Cu(III) analog of the Gilman reagent, has been prepared in high yield from halo-Gilman reagents Me(2)CuLi.LiX (X = Cl, Br, I) and 2,3-dichloropropene and found to have surprising thermal stability. The cyano-Gilman reagent (X = CN) follows a different pathway.