Chiral sodium complex-catalyzed asymmetric cascade cycloaddition/hydration/1,2-rearrangement.

The research on the coordination chemistry and catalytic applications of sodium ions is of great importance. Inspired by the sodium ions-activated enzymes, we explored a sodium complex based on the synergistic coordination of polyfluorophosphate anions and water molecules. X-ray crystallography and computational chemistry revealed its unique spatial structure and highlighted the activation state of the water molecules within the chiral cavity. Furthermore, we have successfully applied the sodium complex in the catalysis of α-ketoimine-type 1,2-rearrangement, overcoming challenges of background reaction and competitive inhibition, ultimately achieving the construction of a series of chiral N-fused polycyclic isoquinolines with remarkable enantioselectivity. Mechanism studies shown that sodium complex activate and regulate water molecules to achieve highly stereoselective hydration process in the chiral environment and generate the key chiral 1,2-diol intermediate. Our research brings insights into the design and application of group 1 metal complexes and provides an approach to the development of asymmetric 1,2-rearrangement reactions.