UC Santa Barbara

Over the past twenty years, asymmetric gold(I)-catalysis has remained challenging due to the inherent linear structure of gold(I) complexes. The Zhang group has made significant advances in addressing this challenge via the development of ligand-enabled cooperative homogeneous gold catalysis for the past decade. However, cumbersome ligand synthesis limits the scope of available ligands and hinders further exploration of asymmetric catalysis. In my graduate research, a new and divergent synthesis of chiral bifunctional binaphthyl-2-ylphosphines was developed. This method enables the rapid construction of a chiral bifunctional gold catalyst library, including 23 new catalysts. With this catalyst library, asymmetric dearomatization of naphthols and phenols was achieved to access chiral spiro carbocycles with excellent enantioselectivities. Furthermore, we developed enantioselective desymmetrization and parallel kinetic resolution of ethynylcyclobutanols, leading to the synthesis of chiral α-methylenecyclopentanones. Extending beyond asymmetric gold catalysis, we also introduced a gold-catalyzed stererospecific trans-hydrogenation of internal alkynes, facilitated by a key hydrosilane-Lewis base interaction.