Recently, Associate Professor Tilong Yang at the College of Chemistry and Environmental Engineering, Shenzhen University, in collaboration with Professor Xumu Zhang’s group at the Southern University of Science and Technology, reported new progress in earth-abundant-metal-catalyzed asymmetric hydrogenation and mechanistic studies. The work, entitled “Cobalt-Catalyzed Desymmetrizing Hydrogenation of Cyclic Anhydrides,” was published in Angewandte Chemie International Edition. Associate Professor Tilong Yang served as a co-corresponding author, and Sixian Lai, a 2025 master’s student at the College of Chemistry and Environmental Engineering, Shenzhen University, contributed to the theoretical calculations.

    The γ- and δ-Lactones are important structural motifs commonly found in pharmaceuticals and natural products. Asymmetric hydrogenation of cyclic anhydrides provides an atom-economical approach to their efficient synthesis. However, conventional inner-sphere hydrogenation mechanisms based on precious-metal catalysts often rely strongly on substrate coordination and precise steric matching, which can limit substrate generality. To address this challenge, the research team developed an earth-abundant cobalt-catalyzed desymmetrizing hydrogenation of cyclic diacid anhydrides, expanding the substrate scope and enabling efficient conversion of structurally diverse substrates.

    Theoretical calculations and mechanistic studies indicate that the key feature of this reaction lies in the distinctive electronic structure of a d⁷ Co(II) dihydride species, which enables an outer-sphere hydride-transfer mode distinct from those typically associated with precious-metal catalysis and reduces the dependence on direct substrate–metal coordination and stringent geometric matching. The resulting relatively flexible chiral environment facilitates both effective stereocontrol and broader substrate compatibility, highlighting the unique role of first-row transition-metal electronic structure in governing reaction pathways and selectivity. This study provides new mechanistic insight into asymmetric hydrogenation catalyzed by earth-abundant metals and offers a theoretical basis for the design of broadly applicable catalytic systems guided by electronic-structure and orbital considerations.

Paper link: https://doi.org/10.1002/anie.6111891