Racemic pyrrolin‐4‐ones, accessible from α‐amino acids, undergo asymmetric stereoselective organocatalyzed 1,4‐additions to trans‐β‐nitrostyrenes (up to 98 % ee; dr up to 97:3). From a series of typical organocatalysts, the best performance was achieved using (+)‐camphor‐1,3‐diamine‐derived bifunctional organocatalysts. A broad substrate scope and some follow‐up modifications have been demonstrated.magnified image

In the synergistic dual catalytic process, the kinetics of the catalytic cycles must be balanced for the successful outcome of the reaction. Therefore, the analysis of the kinetics of the independent catalytic cycles is essential for such reactions, as it enables their relational optimization as well as their design. Here we describe an analysis of the mechanism of a catalytic synergistic bimetallic reaction through the experimental study of a palladium-catalysed cross-coupling of aryl halides with terminal alkynes, an example of a monometallic dual catalytic process. The proposed mechanism of the investigated reaction was disassembled into two palladium catalytic cycles and further into elementary reactions, and each step was studied independently. The described mechanistic analysis allowed us to identify the rate-determining step of the catalytic process by comparing the rates of the elementary reactions under similar reaction conditions, balanced kinetics of the palladium catalytic cycles, and also in which step which reagent enters the catalytic cycle and how.