Catalytic Asymmetric Construction of Nonadjacent Stereoelements

Abstract Nonadjacent chiral scaffolds are privileged motifs in bioactive molecules and medicines, which have stimulated chemists’ ingenuity in achieving the asymmetric construction of non‐contiguous chiral elements directly. Current strategies include bifunctional catalysis, synergistic catalysis, cascade catalysis and others, enabling the production of a wide range of enantiomerically enriched compounds featuring different combinations of nonadjacent chirality, including multiple elements of central chirality, central and allenyl axial chirality, and central and biaryl axial chirality. As compared to the patterns of multiple nonadjacent elements of central chirality, the latter two are less frequently reported. This minireview aims to summarize the key developments in reaction design, mechanistic studies, and synthetic applications, with the goal of stimulating further exploration in this important area of asymmetric catalysis.