We report an efficient method for synthesizing 1-methyl-1H-indole-3-carboxylates with cross-dehydrogenative coupling. However, the coupling reactions are a way to functionalize the α carbon of an iminium from tertiary amines. The synthesis of 1-methyl-1H-indole-3-carboxylate from N,N-dimethylaniline with bromoacetates has not been reported. In the present work, we describe a novel route for synthesizing 1-methyl-1H-indole-3-carboxylate with N,N-dimethylaniline with a wide range of phenyl bromoacetate derivatives. The features such as simple procedure and good to excellent yields (69-90%) make this method a highly efficient procedure for the preparation of indole derivatives using Cu(OAc)2·H2O as a catalyst in the presence of tert-butyl hydroperoxide.