Practical Catalytic Cleavage of C(sp(3))−C(sp(3)) Bonds in Amines

The selective cleavage of thermodynamically stable C(sp(3))−C(sp(3)) single bonds is rare compared to their ubiquitous formation. Herein, we describe a general methodology for such transformations using homogeneous copper‐based catalysts in the presence of air. The utility of this novel methodology is demonstrated for C(α)−C(β) bond scission in >70 amines with excellent functional group tolerance. This transformation establishes tertiary amines as a general synthon for amides and provides valuable possibilities for their scalable functionalization in, for example, natural products and bioactive molecules.