Making and Breaking of C−N Bonds: Applications in the Synthesis of Unsymmetric Tertiary Amines and α‐Amino Carbonyl Derivatives.

An operationally simple process has been developed for the synthesis of unsymmetrical amines and α‐amino carbonyl derivatives in the absence of a catalyst, ligand, oxidant, or any additives. Contrary to known reductive amination methods, this protocol is amenable to substrates containing other reducible groups. This process effectively results in consecutive cleavage and formation of C−N bonds. DFT studies and Hammett analysis provide useful insight into the mechanism. The role of noncovalent interactions as a stabilizing factor have been examined in the protocol. A wide range of alkyl‐bromides have been coupled efficiently with a variety of dimethyl anilines to get unsymmetric tertiary amines with yields up to 90%. This methodology was further extended to the synthesis of α‐amino carbonyl derivatives with yields up to 93%. [ABSTRACT FROM AUTHOR]