Recent advances in chiral aluminum asymmetric catalysis: ligand design, coordination modulation, and structure–activity relationships

The development of sustainable strategies for asymmetric catalysis remains a central goal in modern synthetic chemistry. Chiral aluminum catalysts, derived from earth-abundant and low-toxicity main-group elements, are emerging as powerful alternatives to precious transition-metal systems. This review systematically surveys two decades of progress in chiral aluminum asymmetric catalysis, with a central focus on the fundamental correlation between rational ligand design, coordination environment tuning at aluminum centers, and the resulting structure–activity/selectivity relationships. We highlight how modular ligand engineering including 1,1'-binaphthyl-2,2'-diol (BINOL), salen, and N-heterocyclic scaffolds enables precise control over aluminum’s coordination geometry, Lewis acidity, and chiral microenvironment, delivering high enantio- and regiocontrol across diverse reactions from cycloadditions and asymmetric reductions to C–H functionalization and stereoselective polymerization. Beyond their cost and environmental advantages, these systems showcase unique stereocontrol mechanisms arising from metal-centered chirality and cooperative catalysis. Challenges remain in expanding substrate scope and improving recyclability, but continued innovation promises to establish aluminum catalysis as a frontier platform for the sustainable synthesis of pharmaceuticals, fine chemicals, and functional materials.