ORTHO FUNCTIONALIZATION OF AROMATIC-AMINES - ORTHO LITHIATION OF N-PIVALOYLANILINES

A method is described to convert N-pivaloylanilines and toluidines into their o-lithio and o-(lithiomethyl) derivatives, respectively. These species, in particular those derived from p-chloro-, m-methoxy-, and o-methylaniline, react with a variety of electrophiles (dimethyl disulfide, methyl iodide, DMF, benzaldehyde, trimethylsilyl chloride, acetaldehyde, CO2) to give ortho-substituted derivatives in very good yield. N-Pivaloyl-m-anisidine can be functionalized regiospecifically in the 2 position. The pivalamido function is slightly superior to a methoxyl group as an ortho director. © 1979, American Chemical Society. All rights reserved.