A convenient synthetic approach for the synthesis of α‐oxo‐acetamidines via copper‐catalyzed C(sp3)‐H amidination has been developed. This approach allows the direct amidination of three C(sp3)‐H bonds without cyclization.Methyl ketones and primary and secondary amines are tolerant and afford the corresponding products in moderate to good yields. Furthermore, this protocol is also applicable to the synthesis of unsymmetrical α‐oxo‐acetamidines via one‐pot, multicomponent reactions (MCRs).

A convenient method for the synthesis of 2-oxo-acetamidines from methyl ketones using aromatic amines and DMF as nitrogen sources is reported via copper-catalyzed C(sp 3 )-H amidination. Various methyl ketones react readily with aromatic amines and DMF, producing 2-oxo-acetamidines in yields of 47 to 92%. This protocol features the simultaneous formation of C-N and C]N bonds using DMF and aromatic amines as two different nitrogen sources. It thus provides an efficient approach to construct acyclic amidines via three C(sp 3 )-H bond amidination. Based on the preliminary experiments, a plausible mechanism of this transformation is disclosed.