Asymmetric Catalysis Promoted by Hierarchical Chirality of Metal Nanoclusters

• • Enantioselective allylic alkylation catalyzed by chiral palladium nanoparticles achieved ee values up to 99% (Jansat et al., J Am Chem Soc, 2004, 126: 1592–1593), demonstrating that nanoparticle surfaces can enforce high stereocontrol, which is critical for reducing costly chiral resolution steps in pharmaceutical manufacturing. • • Asymmetric Suzuki-Miyaura coupling catalyzed by chiral palladium nanoparticles proceeded at room temperature with ee values reaching 99% (Sawai et al., Angew Chem Int Ed, 2008, 47: 6917–6919), enabling energy-efficient production of axially chiral biaryls relevant to agrochemical and pharmaceutical intermediates. • • Rhodium-catalyzed asymmetric 1,4-addition of aryl- and alkenylboronic acids to enones achieved ee values up to 99% (Takaya et al., J Am Chem Soc, 1998, 120: 5579–5580), establishing a benchmark for C–C bond formation with precise stereochemical control that remains industrially relevant for chiral building blocks. • • Enantioseparation of Au20(PP3)4Cl4 clusters with intrinsically chiral cores was accomplished (Zhu et al., Angew Chem Int Ed, 2018, 57: 9059–9063), providing a rare example of core-based chirality in metal NCs and enabling mechanistic studies that link structural hierarchy to catalytic enantioselectivity.