The [3+2] annulation of trifluoromethylated ketimines with acrylates has been enabled by rhenium-catalyzed C–H activation, delivering a variety of β-CF3 β-amino esters. The reaction has exhibited broad substrate generality regarding aromatic CF3-ketimines and acrylates, the ability for gram scale synthesis, and facile derivation of the annulation products. The transformation is one of the few examples
acyclic CF3-ketimines have been engaged in 1,3-cycloaddition reactions. The capability for gram-scale synthesis and variant derivatizations of cycloaddition adducts illustrates the synthetic potential of this approach. This protocol provides a facile access to a rapidly enlarging pool of motifs with a trifluoromethylated fully substituted carbon.