Chiral-at-metal catalysts: history, terminology, design, synthesis, and applications.

For decades, advances in chiral transition metal catalysis have been closely tied to the development of customized chiral ligands. Recently, however, an alternative approach to this traditional metal-plus-chiral-ligand method has emerged. In this new strategy, chiral transition metal catalysts are composed entirely of achiral ligands, with the overall chirality originating exclusively from a stereogenic metal center. This "chiral-at-metal" approach offers the benefit of structural simplicity. More importantly, by removing the need for chiral elements within the ligand framework, it opens up new possibilities for designing innovative catalyst architectures with unique properties. As a result, chiral-at-metal catalysis is becoming an increasingly important area of research. This review offers a comprehensive overview and detailed insights into asymmetric chiral-at-metal catalysis, encouraging scientists to explore new avenues in asymmetric transition metal catalysis and driving innovation in both fundamental and applied research.