Axially Chiral Styrene-Based Organocatalysts: Structure–Activity Relationship, Density Functional Theory Calculations and Application

In this work, a detailed discussion of the design, synthesis, and structure-activity relationships of a novel class of axially chiral styrene-based organocatalysts was posted, successfully achieving the efficient asymmetric synthesis of sulfone-containing axially chiral styrenes. It was found that the dual chiral units in the catalyst operate through a synergistic mechanism: the <i>R</i>-configured axially chiral framework enables stereospatial recognition via π-π stacking, while the (<i>S</i>, <i>S</i>)-squaramide unit locks the conformation of the reaction intermediate through a multiple hydrogen-bonding network. Together, they confer excellent enantioselectivity to the key proton migration step, establishing the structural basis for the reaction's effective stereocontrol.