Accessing Non-Conventional Chiral Architectures via Enantioselective Gold Catalysis

Chirality in organic molecules extends beyond classical tetrahedral stereocenters to axial, planar, and inherently chiral architectures, where stereochemical information is encoded in conformational or topological features. The enantioselective construction of these non-conventional chiral elements remains a key challenge in asymmetric catalysis.1 Chiral gold(I) catalysis offers a powerful yet underexplored platform, combining π-activation with efficient stereocontrol enabled by tailored ligand design.2 This contribution highlights our recent advances in enantioselective gold catalysis toward structurally diverse frameworks displaying unconventional chirality. In particular, transformations leading to conformationally constrained indole-fused diazocines and inherently chiral calix[4]arenes3 will be discussed. These studies underscore the potential of gold catalysis to control multiple chiral elements and access complex architectures with high stereoselectivity.