Atroposelective Construction of Axially Chiral Tetraarylethenes Via NHC‐Catalyzed Desymmetrization

ABSTRACT We report the first NHC‐catalyzed atroposelective synthesis of axially chiral tetraarylethenes (TAEs) via oxidative desymmetrization of prochiral TAE dialdehydes. This catalytic strategy operates under mild conditions and accommodates a broad range of phenolic and nitrogen nucleophiles, delivering diverse axially chiral TAEs in good yields and up to 99% ee. The method features excellent functional‐group tolerance, enables late‐stage modification of complex natural products and pharmaceuticals, and is readily scalable. Furthermore, the resulting axially chiral TAEs display distinct photophysical behavior, pronounced aggregation‐induced emission (AIE), and strong circularly polarized luminescence (CPL). This work establishes a general and efficient platform for constructing functional chiral TAEs with promising optoelectronic potential.