Introduction
In the fifty years since being discovered, the Pauson–Khand reaction (PKR) has transformed the design and synthesis of ring-fused cyclopentenones – an unsaturated motif of immense value for building complex molecular compounds. Moreover, the PKR is frequently used in natural product synthesis, owing to the predictable and high diastereoselectivity afforded by this cyclocarbonylation reaction. And yet, the scope of the asymmetric PKR remains limited. This presentation will be on the discoveries made in our research group that led to the expansion of the scope of the Rh(I)-catalyzed asymmetric PKR through catalyst-controlled reactivity modes. Moreover, the application of our findings to the synthesis of the medicinally important target thapsigargin will be highlighted.